Dyeing composition for human keratinous fibres with direct dyes and dicationic compounds

ABSTRACT

The present disclosure relates to a composition for dyeing human keratin fibers, such as the hair, comprising, in a medium suitable for dyeing, at least one direct dye and at least on dicationic compound. Also disclosed herein is a process for dyeing and lightening human keratin fibers, such as the hair, with the compositions disclosed, as well as a the corresponding dyeing kits.

The present invention relates to a dye composition for human keratinfibers, and more particularly the hair, comprising at least one directdye and also at least one dicationic compound in a medium that issuitable for dyeing.

It is known practice to dye human keratin fibers, and in particular thehair, with dye compositions containing direct dyes, in particularnitrobenzene dyes, acidic azo dyes, cationic azo dyes, anthraquinonedyes and natural dyes.

These colorations may be performed by applying the compositioncontaining the direct dye(s) directly onto the keratin fibers, or byapplying a mixture, prepared extemporaneously, of a compositioncontaining the direct dye(s) with a composition containing an oxidizingbleaching agent, which is preferably aqueous hydrogen peroxide solution.In this case, this process is termed lightening direct dyeing.

However, when they are incorporated into dye compositions, direct dyeshave the drawback of leading to colorations that show insufficientfastness, in particular with respect to shampooing.

Certain di- or tricationic dyes have already been described and proposedfor coloring paper; cationic diazomethines or triazomethines have thusbeen described in European patent no. 318 294 B1, and cationic azo- ordiazoimidazoles have also been described in U.S. Pat. Nos. 5,708,151 and5,674,299.

Moreover, European patent application no. 1 133 975 A2 discloses a hairdye composition especially comprising a direct dye having the followingstructure:

The Applicant has now discovered that it is possible to obtain noveldyes capable of producing strong colorations, which show littleselectivity and good resistance to the various attacking factors towhich the hair may be subjected, by combining a conventional direct dyewith at least one suitably selected dicationic compound.

This discovery forms the basis of the present invention.

Now, after considerable research conducted in this matter, the Applicanthas discovered that it is possible to obtain dye compositions with knowndirect dyes, which make it possible to obtain shades that show goodresistance to the various attacking factors to which the hair may besubjected (light, bad weather, washing, permanent-waving, perspirationand rubbing) and in particular to shampooing, if dicationic compoundschosen from those of formulae (I), (II) (III) and (IV) described beloware introduced into said dye compositions.

The shades obtained with said combinations of dyes are moreover strong,chromatic (luminous) and show little selectivity, i.e. they producesmall differences in coloration along the same length of keratin fiber,which may in fact be differently sensitized (i.e. damaged) between itsend and its root.

These discoveries form the basis of the present invention.

A first subject of the present invention is thus a composition fordyeing human keratin fibers, and more particularly the hair, comprisingat least one direct dye in a medium that is suitable for dyeing,characterized in that it also comprises at least one dicationic compoundchosen from those of formula (I), (II) or (III) described below, and adye composition for human keratin fibers, and more particularly thehair, comprising, in a medium that is suitable for dyeing, at least onedicationic compound of formula (IV) defined below and at least onedirect dye different than the group formed by the basic dyes generallyreferred to in the field of coloration as “BASIC DYES”, including BasicBlue 7 (C.I. 42595), Basic Blue 26 (C.I. 44045), Basic Blue 99 (C.I.56059), Basic Violet 10 (C.I. 45170), Basic Violet 14 (C.I. 42515),Basic Brown 16 (C.I. 12250), Basic Brown 17 (C.I. 12251), Basic Red 2(C.I. 50240), Basic Red 22 (C.I. 11055), Basic Red 76 (C.I. 12245),Basic Red 118 (C.I. 12251:1), Basic Yellow 57 (C.I. 12719).

Another subject of the invention relates to a ready-to-use compositionfor dyeing human keratin fibers, and in particular the hair, whichcontains at least one direct dye, at least one dicationic compound offormula (I), (II), (III) or (IV), and an oxidizing agent.

For the purposes of the invention, the term “ready-to-use composition”means the composition intended to be applied in unmodified form to thekeratin fibers, i.e. it may be stored in unmodified form before use ormay result from the extemporaneous mixing of two or more compositions.

The invention is also directed toward a process for the direct dyeing ofhuman keratin fibers, and in particular the hair, which consists inapplying to the fibers a composition containing, in a medium that issuitable for dyeing, at least one direct dye and at least one dicationiccompound of formula (I), (II), (III) or (IV).

The invention is also directed toward a process for the lighteningdirect dyeing of human keratin fibers, and in particular the hair, whichconsists in applying to the fibers an extemporaneous mixture of acomposition containing, in a medium that is suitable for dyeing, atleast one direct dye and at least one dicationic compound of formulae(I), (II), (III) and (IV) and a composition containing at least oneoxidizing agent.

A subject of the invention is also a device for the lightening directdyeing of human keratin fibers, and in particular the hair, or a dyeing“kit”, which comprises a first compartment containing, in a medium thatis suitable for dyeing, at least one direct dye and at least onedicationic compound of formula (I), (II), (III) or (IV), and a secondcompartment containing an oxidizing agent.

This device may be equipped with a means for applying the desiredmixture to the hair, such as the devices described in patent FR-2 586913 in the name of the Applicant.

However, other characteristics, aspects, subjects and advantages of theinvention will emerge even more clearly on reading the description andthe examples that follow.

Dicationic Direct Dye

The dicationic direct dyes according to the present invention are chosenfrom those of formula (I), (II), (III) or (IV) below:

in which formula (I) or (II):

-   -   A and A1, independently of each other, denote a radical of        formula (a) below

-   -   Z denotes an aliphatic or aromatic radical,    -   Z₁ denotes an alkyl radical,    -   R₁ and R₂, independently of each other, denote a hydrogen atom        or a (C₁–C₄)alkyl radical, or a (C₁–C₄)alkyl radical substituted        with one or more halogen atoms, a hydroxyl, carboxyl or cyano        radical, a (C₁–C₄)alkoxy radical, a (C₁–C₄)alkoxy radical        substituted with one or more hydroxyl or (C₁–C₄)alkoxy radicals,        or an amino, alkylamino, dialkylamino, aminocarbonyl, phenyl,        phenoxy or phenylaminocarbonyl radical, in which the phenyl        radical is unsubstituted or substituted with a (C₁–C₄)alkyl,        (C₁–C₄)alkoxy or phenoxy radical, or R₁ and R₂ form, together        with the two nitrogen atoms that bear them and the radical Z, a        piperazine ring,    -   X is a bridging radical chosen from: —CO—; —CO—CH₂—CH₂—CO—;        —CO—CO—; 1,4-dicarbonylphenyl; —CH₂—CH₂—; or a triazine of        formula (b) or (c) below:

in which:

-   -   Y and Y1, independently of each other, denote a halogen atom or        a hydroxyl, amino, monoalkylamino, dialkylamino, 1-piperidino,        morpholino or 1-piperazino radical, the piperazino radical being        unsubstituted or substituted on the nitrogen atom not attached        to the triazine ring with a (C₁–C₄)alkyl radical, said alkyl        radicals being unsubstituted or substituted with hydroxyl,        amino, mono(C₁–C₄)alkylamino or di(C₁–C₄) alkylamino,    -   Z₂ denotes a (C₂–C₈)alkylene radical or forms a piperazine ring        with the two adjacent nitrogen atoms and the radicals R₁ and R₂,    -   in the radical of formula (a),    -   R₃ and R₄, independently of each other, denote a hydrogen atom        or a (C₁–C₄)alkyl radical, or (C₁–C₄)alkyl substituted with one        or more halogen atoms, a hydroxyl, carboxyl, or cyano radical, a        (C₁–C₄)alkoxy radical, a (C₁–C₄)alkoxy radical substituted with        a hydroxyl or (C₁–C₄)alkoxy radical, or an amino, alkylamino,        dialkylamino, aminocarbonyl, phenyl, phenoxy or        phenylaminocarbonyl radical, in which the phenyl radical is        unsubstituted or substituted with a (C₁–C₄)alkyl, (C₁–C₄)alkoxy        or phenoxy radical,    -   R₅ and R₆, independently of each other, denote a hydrogen atom,        a (C₁–C₄)alkyl or (C₁–C₄)alkoxy radical optionally substituted        with a hydroxyl, carboxyl, halogen or cyano radical, a        (C₁–C₄)alkoxy radical optionally substituted with a hydroxyl or        (C₁–C₄)alkoxy radical, or an amino, alkylamino, dialkylamino,        aminocarbonyl, phenyl, phenoxy or phenylaminocarbonyl radical,        in which the phenyl radical is unsubstituted or substituted with        a (C₁–C₄)alkyl, (C₁–C₄)alkoxy or phenoxy radical,    -   An⁻ denotes an anion.

Preferably, according to the invention, in formula (I),

-   -   R₁ and R₂, independently of each other, denote hydrogen,        (C₁–C₄)alkyl substituted with hydroxyl or (C₁–C₄)alkoxy, and        even more particularly denote hydrogen or methyl,    -   Z denotes a linear, branched or cyclic C₂–C₈ alkyl radical        optionally substituted with a hydroxyl, alkoxy or halogen, the        chain of said radical optionally being interrupted with a group        —O— or —NR₁—; a 1,4-phenyl radical, a 1,4-naphthyl radical        optionally substituted with an alkyl, alkoxy or halogen; Z        possibly forming a piperazine ring with R₁, R₂ and the 2        nitrogen atoms,    -   Z preferably denotes an unsubstituted phenyl radical, a phenyl        or naphthyl radical substituted with 1 or 2 methyl or methoxy        radicals, a piperazine radical by bonding with R₁, R₂ and the 2        nitrogen atoms, or a (C₂–C₄)alkylene radical which is        unsubstituted or substituted with one or two hydroxyls,    -   X denotes a group of formula (b).

Preferably, according to the invention, in formula (II),

-   -   Z₁ denotes a linear, branched or cyclic C₂–C₈ alkyl radical,        optionally substituted with a hydroxyl, alkoxy or halogen, the        chain of said radical optionally being interrupted with a group        —O— or —NR₁—; a piperazine ring formed with R₁, R₂ and the two        nitrogen atoms,    -   Z₁ preferably denotes a (C₂–C₆)alkylene radical which is        unsubstituted or substituted with one or more hydroxyl, a        piperazine ring formed with R₁, R₂ and the two nitrogen atoms;        and even more particularly an unsubstituted (C₂–C₄)alkylene        radical,    -   R₃ and R₄ denote methyl or ethyl, and R₅ and R₆ denote hydrogen,        methyl or methoxy.

in which formula (III),

-   -   the number of cationic charges is two,    -   X′ and Y′, independently of each other, denote hydrogen,        halogen, (C₁–C₄)alkyl, (C₁–C₄)alkoxy,        (C₁–C₄)-alkylcarbonylamino, arylcarbonylamino, ureido or        arylureido,    -   R′₁ denotes hydrogen, a substituted alkyl or aryl radical, an        unsubstituted alkyl or aryl radical, or the same meaning as R′₂    -   R′₂ is a radical of formula (d) below:

in which:

-   -   B denotes a linear or branched alkylene radical,    -   R′₆ denotes hydrogen or substituted or unsubstituted alkyl,    -   R′₇ and R′₈, independently of each other, denote substituted or        unsubstituted alkyl,    -   R′₆ and R′₇, together with the nitrogen, form a substituted or        unsubstituted 5-, 6- or 7-membered ring, which may contain other        hetero atoms, or alternatively R′₆, R′₇ and R′₈ together form a        pyridinium ring,    -   R′₃ denotes hydrogen, halogen, (C₁–C₄)alkyl or (C₁–C₄)-alkoxy,    -   W is a radical of formula (e) below:

in which:

-   -   K is a coupling radical,    -   Z denotes a bridging radical chosen from the radicals of        formulae:

or —CO—NR′₉—B₁—NR′₉—CO—,

-   -   and in which R′₉ denotes hydrogen or unsubstituted or        substituted (C₂–C₄)alkylene, the alkylene radical being linear        or branched and possibly being interrupted with one or more        groups chosen from: —NR′9—, —O— and —S—.

Preferably, according to the invention, in formula (III),

-   -   B denotes ethylene, n-propylene, isopropylene or n-butylene,    -   K denotes a coupling compound chosen from those of formula        (f), (g) or (h) below

in which,

-   -   X′, Y′ and R′₁ and R′₂ have the same meaning as in formula        (III),    -   n is equal to 1 or 2,    -   K₁ denotes the radical of formula:

in which formula (IV) the groups of formula —NH-A-CH═CH—B are identicalor different and in which,

-   -   A denotes a substituted or unsubstituted benzene ring,    -   B denotes a radical derived from a heterocyclic compound        containing quaternized nitrogen comprising an active methyl or        methylene radical,    -   R denotes the residue of a crosslinking agent chosen from        phosgene, halogenated triazines and halogenated pyrimidines.

More particularly, each group B may denote a quinolinium, picolinium,benzothiazolium, benzimidazolium, indolium or quinoxalinium derivative;each group A may denote a benzene ring that is unsubstituted orsubstituted with one or more radicals chosen from (C₁–C₄)alkoxy,(C₁–C₄)alkyl or halogen; and R denotes a halogenated triazine chosenfrom 2,4,6-trichlorotriazine, 2,4,6-trifluorotriazine,2,4-dichloro-6-(dimethylaminopropylamino)triazine,2,4-dichloro-6-hydroxytriazine,2,4-difluoro-6-(trimethylaminoethylamino)triazine chloride,2,4-difluoro-6-(N-carboxymethylamino)triazine,2,4-dichloro-6-(N,N-dihydroxyethylamino)triazine,2,4-difluoro-6-(N-hydroxypropylamino)triazine,2,4-dichloro-6-(N,N-dimethylamino)triazine,2,4-difluoro-6-(N,N-dihexylamino-triazine and2,4-dichloro-6-(N-2-sulfoethylamino)triazine.

According to the present invention, among the compounds of formula (I)that may be mentioned more particularly is the compound sold by thecompany CIBA under the name Pergasol Violet F-R, having the followingformula:

Mention may also be made of the compounds of formula (I) correspondingto formulae (I)2 to (I)7 below:

According to the present invention, among the compounds of formula (III)that may be mentioned more particularly is the compound sold by thecompany CIBA under the name Pergasol Orange F-3G, having the followingformula:

According to the present invention, among the compounds of formula (IV)that may be mentioned more particularly is the compound sold by thecompany Ciba under the name Pergasol Jaune F-6G, having the followingformula:

The dyes of formula (I), (II), (III) and (IV) according to the presentinvention are known per se, and are described and prepared in patentsEP-0 318 294 B1 or U.S. Pat. No. 5,674,299 or U.S. Pat. No. 5,708,151,the content of which forms an integral part of the present invention.

They are generally present in the dye composition in proportions rangingfrom about 0.01% to 40% and preferably from about 0.1% to 20% by weightrelative to the total weight of the composition.

Direct Dyes

The direct dyes that may be used according to the invention may bechosen, in a nonlimiting manner, for example, from neutral, acidic orcationic nitrobenzene direct dyes, neutral, acidic or cationic azodirect dyes, cationic direct dyes comprising a quaternized nitrogen atomand a —CH═N— bond, quinone direct dyes and in particular, neutral,acidic or cationic anthraquinones, azine direct dyes, triarylmethanedirect dyes, indoamine direct dyes and natural direct dyes.

Among the benzene direct dyes that may be used according to theinvention, mention may be made especially of the following compounds:

-   -   1,4-diamino-2-nitrobenzene    -   1-amino-2-nitro-4-β-hydroxyethylaminobenzene    -   1-amino-2-nitro-4-bis(β-hydroxyethyl)aminobenzene    -   1,4-bis(β-hydroxyethylamino)-2-nitrobenzene    -   1-β-hydroxyethylamino-2-nitro-4-bis(β-hydroxyethylamino)benzene    -   1-β-hydroxyethylamino-2-nitro-4-aminobenzene    -   1-β-hydroxyethylamino-2-nitro-4-(ethyl)(β-hydroxyethyl)aminobenzene    -   1-amino-3-methyl-4-β-hydroxyethylamino-6-nitrobenzene    -   1-amino-2-nitro-4-β-hydroxyethylamino-5-chlorobenzene    -   1,2-diamino-4-nitrobenzene    -   1-amino-2-β-hydroxyethylamino-5-nitrobenzene    -   1,2-bis(β-hydroxyethylamino)-4-nitrobenzene    -   1-amino-2-tris(hydroxymethyl)methylamino-5-nitrobenzene    -   1-hydroxy-2-amino-5-nitrobenzene    -   1-hydroxy-2-amino-4-nitrobenzene    -   1-hydroxy-3-nitro-4-aminobenzene    -   1-hydroxy-2-amino-4,6-dinitrobenzene    -   1-β-hydroxyethyloxy-2-β-hydroxyethylamino-5-nitrobenzene    -   1-methoxy-2-β-hydroxyethylamino-5-nitrobenzene    -   1-β-hydroxyethyloxy-3-methylamino-4-nitrobenzene    -   1-β,γ-dihydroxypropyloxy-3-methylamino-4-nitrobenzene    -   1-β-hydroxyethylamino-4-β,γ-dihydroxypropyloxy-2-nitrobenzene    -   1-β,γ-dihydroxypropylamino-4-trifluoromethyl-2-nitrobenzene    -   1-β-hydroxyethylamino-4-trifluoromethyl-2-nitrobenzene    -   1-β-hydroxyethylamino-3-methyl-2-nitrobenzene    -   1-β-aminoethylamino-5-methoxy-2-nitrobenzene    -   1-hydroxy-2-chloro-6-ethylamino-4-nitrobenzene    -   1-hydroxy-2-chloro-6-amino-4-nitrobenzene    -   1-hydroxy-6-bis(β-hydroxyethyl)amino-3-nitrobenzene    -   1-β-hydroxyethylamino-2-nitrobenzene    -   1-hydroxy-4-β-hydroxyethylamino-3-nitrobenzene

Among the azo direct dyes that may be used according to the invention,mention may be made of the cationic azo dyes described in patentapplications WO 95/15144, WO 95/01772 and EP 714 954, the content ofwhich forms an integral part of the invention.

Among these compounds, mention may be made most particularly of thefollowing dyes:

-   -   1-,3-dimethyl-2-[[4-(dimethylamino)phenyl]azo]-1H-imidazolium        chloride,    -   1,3-dimethyl-2-[(4-aminophenyl)azo]-1H-imidazolium chloride,    -   1-methyl-4-[(methylphenylhydrazono)methyl]pyridinium methyl        sulfate.

Among the azo direct dyes that may also be mentioned are the followingdyes described in the Colour Index International 3rd edition:

-   -   Disperse Red 17    -   Acid Yellow 9    -   Acid Black 1    -   Basic Red 22    -   Basic Red 76    -   Basic Yellow 57    -   Basic Brown 16    -   Acid Yellow 36    -   Acid Orange 7    -   Acid Red 33    -   Acid Red 35    -   Basic Brown 17    -   Acid Yellow 23    -   Acid Orange 24    -   Disperse Black 9.

Mention may also be made of1-(4′-aminodiphenylazo)-2-methyl-4-[bis(β-hydroxy-ethyl)amino]benzeneand 4-hydroxy-3-(2-methoxyphenylazo)-1-naphthalenesulfonic acid.

Among the quinone direct dyes that may be mentioned are the followingdyes:

-   -   Disperse Red 15    -   Solvent Violet 13    -   Acid Violet 43    -   Disperse Violet 1    -   Disperse Violet 4    -   Disperse Blue 1    -   Disperse Violet 8    -   Disperse Blue 3    -   Disperse Red 11    -   Acid Blue 62    -   Disperse Blue 7    -   Basic Blue 22    -   Disperse Violet 15    -   Basic Blue 99        and also the following compounds:    -   1-N-methylmorpholiniumpropylamino-4-hydroxyanthraquinone    -   1-aminopropylamino-4-methylaminoanthraquinone    -   1-aminopropylaminoanthraquinone    -   5-β-hydroxyethyl-1,4-diaminoanthraquinone    -   2-aminoethylaminoanthraquinone    -   1,4-bis(β, γ-dihydroxypropylamino)anthraquinone

Among the azine dyes that may be mentioned are the following compounds:

-   -   Basic Blue 17    -   Basic Red 2.

Among the triarylmethane dyes that may be used according to theinvention, mention may be made of the following compounds:

-   -   Basic Green 1    -   Acid Blue 9    -   Basic Violet 3    -   Basic Violet 14    -   Basic Blue 7    -   Acid Violet 49    -   Basic Blue 26    -   Acid Blue 7

Among the indoamine dyes that may be used according to the invention,mention may be made of the following compounds:

-   -   2-β-hydroxyethylamino-5-[bis(β-4′-hydroxyethyl)amino]-anilino-1,4-benzoquinone;    -   2-β-hydroxyethylamino-5-(2′-methoxy-4′-amino)anilino-1,4-benzoquinone;    -   3-N(2′-chloro-4′-hydroxy)phenylacetylamino-6-methoxy-1,4-benzoquinoneimine;    -   3-N(3′-chloro-4′-methylamino)phenylureido-6-methyl-1,4-benzoquinoneimine;    -   3-[4′-N-(ethylcarbamylmethyl)amino]phenylureido-6-methyl-1,4-benzoquinoneimine.

Among the direct cationic dyes comprising a quaternized nitrogen atomand a —CH═N— bond, mention may be made of the compounds described inpatent U.S. Pat. No. 5,980,587 and especially those of the followingformulae:

i.e. (1-methyl-1-phenyl)-2(1-methine-4N-methylpyridinylium)hydrazine,chloride or methyl sulfate

i.e.(1-methyl-1-paramethoxyphenyl)-2(1-methine-4N-methylpyridinylium)hydrazine,chloride or methyl sulfate.

Among the natural direct dyes that may be used according to theinvention, mention may be made of lawsone, juglone, alizarin, purpurin,carminic acid, kermesic acid, purpurogallin, protocatechaldehyde,indigo, isatin, curcumin, spinulosin and apigenidin. Extracts ordecoctions containing these natural dyes may also be used, andespecially henna-based poultices or extracts.

The direct dye(s) preferably represent(s) from 0.001% to 20% by weightapproximately, and even more preferably from 0.005% to 10% by weightapproximately, relative to the total weight of the composition.

The medium of the composition that is suitable for dyeing is preferablyan aqueous medium consisting of water and may advantageously containcosmetically acceptable organic solvents including, more particularly,alcohols such as ethyl alcohol, isopropyl alcohol, benzyl alcohol andphenylethyl alcohol, or glycols or glycol ethers such as, for example,ethylene glycol monomethyl, monoethyl and monobutyl ethers, propyleneglycol or its ethers such as, for example, propylene glycol monomethylether, butylene glycol, dipropylene glycol and diethylene glycol alkylethers such as, for example, diethylene glycol monoethyl ether ormonobutyl ether. The solvents may then be present in concentrations ofbetween about 0.5% and 20% and preferably between about 2% and 10% byweight relative to the total weight of the composition.

The dye composition may also contain an effective amount of other agentsthat are previously known elsewhere for direct dyeing, such as variouscommon adjuvants, for instance surfactants that are well known in theprior art and of anionic, cationic, nonionic, amphoteric or zwitterionictype or mixtures thereof, thickeners, antioxidants, fragrances,dispersants, conditioners, especially including cationic or amphotericnonionic polymers, opacifiers, sequestering agents such as EDTA andetidronic acid, UV-screening agents, waxes, volatile or nonvolatile,cyclic, linear or branched silicones, which are possibly organomodified(especially with amine groups), preserving agents, ceramides,pseudoceramides, plant, mineral or synthetic oils, vitamins orprovitamins, for instance panthenol, and nonionic, anionic, amphotericor cationic associative polymers.

Associative Polymers

Associative polymers are water-soluble polymers capable, in an aqueousmedium, of reversibly associating with each other or with othermolecules.

Their chemical structure comprises hydrophilic zones and hydrophobiczones characterized by at least one fatty chain.

Associative Polymers of Anionic Type:

Among these, mention may be made of:

-   -   (I) those comprising at least one hydrophilic unit and at least        one fatty-chain allyl ether unit, more particularly those whose        hydrophilic unit consists of an ethylenic unsaturated anionic        monomer, more particularly a vinylcarboxylic acid and most        particularly an acrylic acid or a methacrylic acid or mixtures        thereof, the fatty-chain allyl ether unit of which corresponding        to the monomer of formula (I) below:        CH₂═CR′CH₂OB_(n)R  (I)        in which R′ denotes H or CH₃, B denotes an ethyleneoxy radical,        n is zero or denotes an integer ranging from 1 to 100, R denotes        a hydrocarbon-based radical chosen from alkyl, arylalkyl, aryl,        alkylaryl and cycloalkyl radicals, containing from 8 to 30        carbon atoms, preferably 10 to 24 carbon atoms and even more        particularly from 12 to 18 carbon atoms. A unit of formula (I)        that is more particularly preferred is a unit in which R′        denotes H, n is equal to 10 and R denotes a stearyl (C₁₈)        radical.

Anionic associative polymers of this type are described and prepared,according to an emulsion polymerization process, in patent EP-0 216 479.

Among these anionic associative polymers that are particularly preferredaccording to the invention are polymers formed from 20% to 60% by weightof acrylic acid and/or of methacrylic acid, from 5% to 60% by weight oflower alkyl (meth)acrylates, from 2% to 50% by weight of fatty-chainallyl ether of formula (I), and from 0% to 1% by weight of acrosslinking agent which is a well-known copolymerizable unsaturatedpolyethylenic monomer, for instance diallyl phthalate,allyl(meth)acrylate, divinylbenzene, (poly)ethylene glycoldimethacrylate or methylenebisacrylamide.

Among the latter polymers, those most particularly preferred arecrosslinked terpolymers of methacrylic acid, of ethyl acrylate and ofpolyethylene glycol (10 EO) stearyl alcohol ether (Steareth-10), inparticular those sold by the company Allied Colloids under the namesSalcare SC 80® and Salcare SC 90®, which are aqueous 30% emulsions of acrosslinked terpolymer of methacrylic acid, of ethyl acrylate and ofsteareth-10 allyl ether (40/50/10).

-   -   (II) those comprising at least one hydrophilic unit of        unsaturated olefinic carboxylic acid type, and at least one        hydrophobic unit of (C₁₀–C₃₀)alkyl ester of unsaturated        carboxylic acid type.

Preferably, these polymers are chosen from those in which thehydrophilic unit of unsaturated olefinic carboxylic acid typecorresponds to the monomer of formula (II) below:

in which R₁ denotes H or CH₃ or C₂H₅, that is to say acrylic acid,methacrylic acid or ethacrylic acid units, and in which the hydrophobicunit of (C₁₀–C₃₀)alkyl ester of unsaturated carboxylic acid typecorresponds to the monomer of formula (III) below:

in which R₂ denotes H or CH₃ or C₂H₅ (that is to say acrylate,methacrylate or ethacrylate units) and preferably H (acrylate units) orCH₃ (methacrylate units), R₃ denoting a C₁₀–C₃₀ and preferably C₁₂–C₂₂alkyl radical.

(C₁₀–C₃₀) alkyl esters of unsaturated carboxylic acids according to theinvention include, for example, lauryl acrylate, stearyl acrylate, decylacrylate, isodecyl acrylate and dodecyl acrylate, and the correspondingmethacrylates, lauryl methacrylate, stearyl methacrylate, decylmethacrylate, isodecyl methacrylate and dodecyl methacrylate.

Anionic polymers of this type are described and prepared, for example,according to U.S. Pat. Nos. 3,915,921 and 4,509,949.

Among the anionic associative polymers of this type that will be usedmore particularly are polymers formed from a monomer mixture comprising:

-   -   (i) essentially acrylic acid,    -   (ii) an ester of formula (III) described above in which R₂        denotes H or CH₃, R₃ denoting an alkyl radical containing from        12 to 22 carbon atoms,    -   (iii) and a crosslinking agent, which is a well-known        copolymerizable polyethylenic unsaturated monomer, for instance        diallyl phthalate, allyl (meth)acrylate, divinylbenzene,        (poly)ethylene glycol dimethacrylate and methylenebisacrylamide.

Among anionic associative polymers of this type that will be used moreparticularly are those consisting of from 95% to 60% by weight ofacrylic acid (hydrophilic unit), 4% to 40% by weight of C₁₀–C₃₀ alkylacrylate (hydrophobic unit) and 0% to 6% by weight of crosslinkingpolymerizable monomer, or alternatively those consisting of from 98% to96% by weight of acrylic acid (hydrophilic unit), 1% to 4% by weight ofC₁₀–C₃₀ alkyl acrylate (hydrophobic unit) and 0.1% to 0.6% by weight ofcrosslinking polymerizable monomer such as those described above.

Among said above polymers, those most particularly preferred accordingto the present invention are the products sold by the company Goodrichunder the trade names Pemulen TR1®, Pemulen TR2® and Carbopol 1382®, andeven more preferentially Pemulen TR1®, and the product sold by thecompany SEPPIC under the name Coatex SX®.

-   -   (III) maleic anhydride/C₃₀–C₃₈ α-olefin/alkyl maleate        terpolymers, such as the product (maleic anhydride/C₃₀–C₃₈        α-olefin/isopropyl maleate copolymer) sold under the name        Performa V 1608® by the company Newphase Technologies.    -   (IV) acrylic terpolymers comprising:    -   (a) about 20% to 70% by weight of a carboxylic acid containing        α,β-monoethylenic unsaturation,    -   (b) about 20% to 80% by weight of a non-surfactant monomer        containing α,β-monoethylenic unsaturation other than (a),    -   (c) about 0.5% to 60% by weight of a nonionic monourethane which        is the product of reaction of a monohydric surfactant with a        monoisocyanate containing monoethylenic unsaturation, such as        those described in patent application EP-A-0 173 109 and more        particularly the terpolymer described in Example 3, namely a        methacrylic acid/methyl acrylate/behenyl        dimethyl-meta-isopropenylbenzylisocyanate ethoxylated (40 EO)        terpolymer, as an aqueous 25% dispersion.    -   (V) copolymers comprising among their monomers a carboxylic acid        containing α,β-monoethylenic unsaturation and an ester of a        carboxylic acid containing α,β-monoethylenic unsaturation and of        an oxyalkylenated fatty alcohol.

Preferentially, these compounds also comprise as monomer an ester of acarboxylic acid containing α,β-monoethylenic unsaturation and of a C₁–C₄alcohol.

An example of a compound of this type which may be mentioned is Aculyn22® sold by the company Rohm & Haas, which is a methacrylic acid/ethylacrylate/stearyl methacrylate oxyalkylenated terpolymer.

Associative Polymers of Cationic Type

According to the present invention, they are preferably chosen fromquaternized cellulose derivatives and polyacrylates containingnon-cyclic amino side groups.

The quaternized cellulose derivatives are in particular:

-   -   quaternized celluloses modified with groups comprising at least        one fatty chain, such as alkyl, arylalkyl or alkylaryl groups        containing at least 8 carbon atoms, or mixtures thereof,    -   quaternized hydroxyethylcelluloses modified with groups        comprising at least one fatty chain, such as alkyl, arylalkyl or        alkylaryl groups containing at least 8 carbon atoms, or mixtures        thereof.

The alkyl radicals borne by the above quaternized celluloses orhydroxyethylcelluloses preferably contain from 8 to 30 carbon atoms. Thearyl radicals preferably denote phenyl, benzyl, naphthyl or anthrylgroups.

Examples of quaternized alkylhydroxyethyl-celluloses containing C₈–C₃₀fatty chains that may be mentioned include the products Quatrisoft LM200, Quatrisoft LM-X 529-18-A, Quatrisoft LM-X 529-18B (C₁₂ alkyl) andQuatrisoft LM-X 529-8 (C₁₈ alkyl) sold by the company Amerchol, and theproducts Crodacel QM, Crodacel QL (C₁₂ alkyl) and Crodacel QS (C₁₈alkyl) sold by the company Croda.

Amphoteric Associative Polymers

These are preferably chosen from polymers comprising at least onenon-cyclic cationic unit. Even more particularly, the ones that arepreferred are those prepared from or comprising 1 to 20 mol % of monomercomprising a fatty chain, preferably 1.5 to 15 mol % and even moreparticularly 1.5 to 6 mol %, relative to the total number of moles ofmonomers.

The amphoteric associative polymers that are preferred according to theinvention comprise, or are prepared by copolymerizing:

-   -   1) at least one monomer of formula (Ia) or (Ib):

in which R₁ and R₂, which may be identical or different, represent ahydrogen atom or a methyl radical, R₃, R₄ and R₅, which may be identicalor different, represent a linear or branched alkyl radical containingfrom 1 to 30 carbon atoms,

-   -   Z represents an NH group or an oxygen atom,    -   n is an integer from 2 to 5,    -   A⁻ is an anion derived from an organic or mineral acid, such as        a methosulfate anion or a halide such as chloride or bromide;    -   2) at least one monomer of formula (II)        RC—CH═CR₇—COOH  (II)        in which R₆ and R₇, which may be identical or different,        represent a hydrogen atom or a methyl radical; and    -   3) at least one monomer of formula (III):        R₆—CH═CR₇—COXR₈  (III)        in which R₆ and R₇, which may be identical or different,        represent a hydrogen atom or a methyl radical, X denotes an        oxygen or nitrogen atom and R₈ denotes a linear or branched        alkyl radical containing from 1 to 30 carbon atoms; at least one        of the monomers of formula (Ia), (Ib) or (III) comprising at        least one fatty chain.

The monomers of formulae (Ia) and (Ib) of the present invention arepreferably chosen from the group consisting of:

-   -   dimethylaminoethyl methacrylate, dimethylaminoethyl acrylate,    -   diethylaminoethyl methacrylate, diethylaminoethyl acrylate,    -   dimethylaminopropyl methacrylate, dimethylaminopropyl acrylate,    -   dimethylaminopropylmethacrylamide,        dimethylaminopropylacrylamide,        these monomers optionally being quaternized, for example with a        C₃–C₄ alkyl halide or a C₁–C₄ dialkyl sulfate.

More particularly, the monomer of formula (Ia) is chosen fromacrylamidopropyltrimethylammonium chloride andmethacrylamidopropyltrimethylammonium chloride.

The monomers of formula (II) of the present invention are preferablychosen from the group consisting of acrylic acid, methacrylic acid,crotonic acid and 2-methylcrotonic acid. More particularly, the monomerof formula (II) is acrylic acid.

The monomers of formula (III) of the present invention are preferablychosen from the group consisting of C₁₂–C₂₂ and more particularlyC₁₆–C₁₈ alkyl acrylates or methacrylates.

The monomers constituting the fatty-chain amphoteric polymers of theinvention are preferably already neutralized and/or quaternized.

The ratio of the number of cationic charges/anionic charges ispreferably equal to about 1.

The amphoteric associative polymers according to the inventionpreferably comprise from 1 mol % to 10 mol % of the monomer comprising afatty chain (monomer of formula (Ia), (Ib) or (III)), and preferablyfrom 1.5 mol % to 6 mol %.

The weight-average molecular weights of the amphoteric associativepolymers according to the invention may range from 500 to 50 000 000 andare preferably between 10 000 and 5 000 000.

The amphoteric associative polymers according to the invention may alsocontain other monomers such as nonionic monomers and in particular suchas C₁–C₄ alkyl acrylates or methacrylates.

Amphoteric associative polymers are described and prepared, for example,in patent application WO 98/44012.

Among the amphoteric associative polymers according to the invention,the ones that are preferred are acrylicacid/(meth)acrylamidopropyltrimethylammonium chloride/stearylmethacrylate terpolymers.

Associative Polymers of Nonionic Type

According to the invention, these are preferably chosen from:

-   -   (1) celluloses modified with groups comprising at least one        fatty chain;    -   examples that may be mentioned include:        -   hydroxyethylcelluloses modified with groups comprising at            least one fatty chain, such as alkyl, arylalkyl or alkylaryl            groups, or mixtures thereof, and in which the alkyl groups            are preferably C₈–C₂₂, for instance the product Natrosol            Plus Grade 330 CS® (C₁₆ alkyls) sold by the company Aqualon,            or the product Bermocoll EHM 100® sold by the company Berol            Nobel,        -   those modified with alkylphenyl polyalkylene glycol ether            groups, such as the product Amercell Polymer HM-1500®            (nonylphenyl polyethylene glycol (15) ether) sold by the            company Amerchol.    -   (2) hydroxypropyl guars modified with groups comprising at least        one fatty chain, such as the product Esaflor HM 22® (C₂₂ alkyl        chain) sold by the company Lamberti, and the products RE210-18®        (C₁₄ alkyl chain) and RE205-1® (C₂₀ alkyl chain) sold by the        company Rhône-Poulenc.    -   (3) copolymers of vinylpyrrolidone and of fatty-chain        hydrophobic monomers; examples that may be mentioned include:        -   the products Antaron V216® or Ganex V216®            (vinylpyrrolidone/hexadecene copolymer) sold by the company            I.S.P.        -   the products Antaron V220® or Ganex V220®            (vinylpyrrolidone/eicosene copolymer) sold by the company            I.S.P.    -   (4) copolymers of C₁–C₆ alkyl methacrylates or acrylates and of        amphiphilic monomers comprising at least one fatty chain, such        as, for example, the oxyethylenated methyl acrylate/stearyl        acrylate copolymer sold by the company Goldschmidt under the        name Antil 208®.    -   (5) copolymers of hydrophilic methacrylates or acrylates and of        hydrophobic monomers comprising at least one fatty chain, such        as, for example, the polyethylene glycol methacrylate/lauryl        methacrylate copolymer.    -   (6) polyurethane polyethers comprising in their chain both        hydrophilic blocks usually of polyoxyethylenated nature and        hydrophobic blocks which may be aliphatic sequences alone and/or        cycloaliphatic and/or aromatic sequences.    -   (7) polymers with an aminoplast ether skeleton containing at        least one fatty chain, such as the Pure Thix® compounds sold by        the company Sud-Chemie.

Preferably, the polyurethane polyethers comprise at least twohydrocarbon-based lipophilic chains containing from 6 to 30 carbonatoms, separated by a hydrophilic block, the hydrocarbon-based chainspossibly being pendent chains, or chains at the end of the hydrophilicblock. In particular, it is possible for one or more pendent chains tobe included. In addition, the polymer may comprise a hydrocarbon-basedchain at one end or at both ends of a hydrophilic block.

The polyurethane polyethers may be multiblock, in particular in triblockform. Hydrophobic blocks may be at each end of the chain (for example:triblock copolymer with a hydrophilic central block) or distributed bothat the ends and in the chain (for example: multiblock copolymer). Thesesame polymers may also be graft polymers or starburst polymers.

The nonionic fatty-chain polyurethane polyethers may be triblockcopolymers in which the hydrophilic block is a polyoxyethylenated chaincomprising from 50 to 1 000 oxyethylene groups. The nonionicpolyurethane polyethers comprise a urethane linkage between thehydrophilic blocks, whence arises the name.

By extension, also included among the nonionic fatty-chain polyurethanepolyethers are those in which the hydrophilic blocks are linked to thelipophilic blocks via other chemical bonds.

As examples of nonionic fatty-chain polyurethane polyethers that may beused in the invention, mention may also be made of Rheolate 205®containing a urea function, sold by the company Rheox, or the Rheolates®208, 204 or 212, and also Acrysol RM 184®.

Mention may also be made of the product Elfacos T210® containing aC₁₂₋₁₄ alkyl chain, and the product Elfacos T212® containing a C₁₈ alkylchain, from Akzo.

The product DW 1206B® from Rohm & Haas containing a C₂₀ alkyl chain anda urethane linkage, sold at a solids content of 20% in water, may alsobe used.

It is also possible to use solutions or dispersions of these polymers,especially in water or in aqueous-alcoholic medium. Examples of suchpolymers that may be mentioned are Rheolate® 255, Rheolate® 278 andRheolate® 244 sold by the company Rheox. The products DW 1206F and DW1206J sold by the company Rohm & Haas may also be used.

The polyurethane polyethers that may be used according to the inventionare in particular those described in the article by G. Fonnum, J. Bakkeand Fk. Hansen—Colloid Polym. Sci 271, 380.389 (1993).

Even more particularly, according to the invention, it is preferred touse a polyurethane polyether that may be obtained by polycondensation ofat least three compounds comprising (i) at least one polyethylene glycolcomprising from 150 to 180 mol of ethylene oxide, (ii) stearyl alcoholor decyl alcohol, and (iii) at least one diisocyanate.

Such polyurethane polyethers are sold especially by the company Rohm &Haas under the names Aculyn 46® and Aculyn 44® [Aculyn 46® is apolycondensate of polyethylene glycol containing 150 or 180 mol ofethylene oxide, of stearyl alcohol and of methylenebis(4-cyclohexylisocyanate) (SMDI), at 15% by weight in a matrix of maltodextrin (4%)and water (81%); Aculyn 44® is a polycondensate of polyethylene glycolcontaining 150 or 180 mol of ethylene oxide, of decyl alcohol and ofmethylenebis(4-cyclohexyl-isocyanate) (SMDI), at 35% by weight in amixture of propylene glycol (39%) and water (26%)].

The associative polymers of nonionic, anionic, cationic or amphoterictype are preferably used in an amount that may vary from about 0.1% to10% by weight relative to the total weight of the dyeing composition.More preferably, this amount varies from about 0.5% to 5% by weight, andeven more preferably from about 1% to 3% by weight.

Cationic Polymers

For the purposes of the present invention, the term “cationic polymer”denotes any polymer containing cationic groups and/or groups that may beionized into cationic groups.

The cationic polymers that may be used in accordance with the presentinvention may be chosen from all those already known per se as improvingthe cosmetic properties of the hair, i.e. especially those described inpatent application EP-A-337 354 and in French patents FR-2 270 846, 2383 660, 2 598 611, 2 470 596 and 2 519 863.

The cationic polymers that are preferred are chosen from thosecontaining units comprising primary, secondary, tertiary and/orquaternary amine groups, which may either form part of the main polymerchain or may be borne by a side substituent directly attached thereto.

The cationic polymers used generally have a number-average molecularmass of between 500 and 5×10⁶ approximately and preferably between 10³and 3×10⁶ approximately.

Among the cationic polymers that may be mentioned more particularly arepolymers of the polyamine, polyamino amide and polyquaternary ammoniumtype.

These are known products. They are described in particular in Frenchpatents Nos. 2 505 348 and 2 542 997. Among said polymers, mention maybe made of:

-   -   (1) homopolymers or copolymers derived from acrylic or        methacrylic esters or amides and comprising at least one of the        units of formula (I), (II), (III) or (IV) below:

in which:

-   -   R₃, which may be identical or different, denote a hydrogen atom        or a CH₃ radical;    -   A, which may be identical or different, represent a linear or        branched alkyl group of 1 to 6 carbon atoms, preferably 2 or 3        carbon atoms, or a hydroxyalkyl group of 1 to 4 carbon atoms;    -   R₄, R₅ and R₆, which may be identical or different, represent an        alkyl group containing from 1 to 18 carbon atoms or a benzyl        radical and preferably an alkyl group containing from 1 to 6        carbon atoms;    -   R₁ and R₂, which may be identical or different, represent        hydrogen or an alkyl group containing from 1 to 6 carbon atoms,        and preferably methyl or ethyl;    -   X denotes an anion derived from an inorganic or organic acid,        such as a methosulfate anion or a halide such as chloride or        bromide.

The polymers of family (1) can also contain one or more units derivedfrom comonomers which may be chosen from the family of acrylamides,methacrylamides, diacetone acrylamides, acrylamides and methacrylamidessubstituted on the nitrogen with lower (C₁–C₄) alkyls, acrylic ormethacrylic acids or esters thereof, vinyllactams such asvinylpyrrolidone or vinylcaprolactam, and vinyl esters.

Thus, among these polymers of family (1), mention may be made of:

-   -   copolymers of acrylamide and of dimethylaminoethyl methacrylate        quaternized with dimethyl sulfate or with a dimethyl halide,        such as the product sold under the name Hercofloc® by the        company Hercules,    -   the copolymers of acrylamide and of        methacryloyloxy-ethyltrimethylammonium chloride described, for        example, in patent application EP-A-080 976 and sold under the        name Bina Quat P 100® by the company Ciba Geigy,    -   the copolymer of acrylamide and of        methacryloyloxy-ethyltrimethylammonium methosulfate sold under        the name Reten® by the company Hercules,    -   quaternized or non-quaternized        vinylpyrrolidone/dialkylaminoalkyl acrylate or methacrylate        copolymers, such as the products sold under the name “Gafquat®”        by the company ISP, such as, for example, “Gafquat® 734” or        “Gafquat® 755”, or alternatively the products known as        “Copolymer® 845, 958 and 937”. These polymers are described in        detail in French patents 2 077 143 and 2 393 573,    -   dimethylaminoethyl        methacrylate/vinylcaprolactam/-vinylpyrrolidone terpolymers,        such as the product sold under the name Gaffix® VC 713 by the        company ISP,    -   vinylpyrrolidone/methacrylamidopropyldimethylamine copolymers        sold in particular under the name Styleze® CC 10 by ISP, and        quaternized vinylpyrrolidone/dimethylaminopropyl methacrylamide        copolymers such as the product sold under the name “Gafquat® HS        100” by the company ISP.    -   (2) Polymers consisting of piperazinyl units and of divalent        alkylene or hydroxyalkylene radicals containing straight or        branched chains, optionally interrupted by oxygen, sulfur or        nitrogen atoms or by aromatic or heterocyclic rings, as well as        the oxidation and/or quaternization products of these polymers.        Such polymers are described, in particular, in French patents 2        162 025 and 2 280 361.    -   (3) Water-soluble polyamino amides prepared in particular by        polycondensation of an acidic compound with a polyamine; these        polyamino amides can be crosslinked with an epihalohydrin, a        diepoxide, a dianhydride, an unsaturated dianhydride, a        bis-unsaturated derivative, a bis-halohydrin, a bis-azetidinium,        a bis-haloacyldiamine, a bis-alkyl halide or alternatively with        an oligomer resulting from the reaction of a difunctional        compound which is reactive with a bis-halohydrin, a        bis-azetidinium, a bis-haloacyldiamine, a bis-alkyl halide, an        epihalohydrin, a diepoxide or a bis-unsaturated derivative; the        crosslinking agent being used in proportions ranging from 0.025        to 0.35 mol per amine group of the polyamino amide; these        polyamino amides can be alkylated or, if they contain one or        more tertiary amine functions, they can be quaternized. Such        polymers are described, in particular, in French patents 2 252        840 and 2 368 508.    -   (4) The polyamino amide derivatives resulting from the        condensation of polyalkylene polyamines with polycarboxylic        acids followed by alkylation with difunctional agents. Mention        may be made, for example, of adipic        acid/dialkylaminohydroxyalkyldialkylenetriamine polymers in        which the alkyl radical contains from 1 to 4 carbon atoms and        preferably denotes methyl, ethyl or propyl. Such polymers are        described in particular in French patent 1 583 363.

Among these derivatives, mention may be made more particularly of theadipic acid/dimethylamino-hydroxypropyl/diethylenetriamine polymers soldunder the name “Cartaretine® F, F4 or F8” by the company Sandoz.

-   -   (5) The polymers obtained by reaction of a polyalkylene        polyamine containing two primary amine groups and at least one        secondary amine group with a dicarboxylic acid chosen from        diglycolic acid and saturated aliphatic dicarboxylic acids        having from 3 to 8 carbon atoms. The molar ratio between the        polyalkylene polyamine and the dicarboxylic acid is between        0.8:1 and 1.4:1; the polyamino amide resulting therefrom is        reacted with epichlorohydrin in a molar ratio of epichlorohydrin        relative to the secondary amine group of the polyamino amide of        between 0.5:1 and 1.8:1. Such polymers are described in        particular in U.S. Pat. Nos. 3,227,615 and 2,961,347.

Polymers of this type are sold in particular under the name “Hercosett®57” by the company Hercules Inc. or alternatively under the name “PD170®” or “Delsette® 101” by the company Hercules in the case of theadipic acid/epoxypropyl/diethylenetriamine copolymer.

-   -   (6) Cyclopolymers of alkyldiallylamine or of        dialkyldiallylammonium, such as the homopolymers or copolymers        containing, as main constituent of the chain, units        corresponding to formula (V) or (VI):

in which formulae k and t are equal to 0 or 1, the sum k+t being equalto 1; R₉ denotes a hydrogen atom or a methyl radical; R₇ and R₈,independently of each other, denote an alkyl group having from 1 to 22carbon atoms, a hydroxyalkyl group in which the alkyl group preferablyhas 1 to 5 carbon atoms, a lower (C₁–C₄) amidoalkyl group, or R₇ and R₈can denote, together with the nitrogen atom to which they are attached,heterocyclic groups such as piperidyl or morpholinyl; R₇ and R₈,independently of each other, preferably denote an alkyl group havingfrom 1 to 4 carbon atoms; Y⁻ is an anion such as bromide, chloride,acetate, borate, citrate, tartrate, bisulfate, bisulfite, sulfate orphosphate. These polymers are described in particular in French patent 2080 759 and in its Certificate of Addition 2 190 406.

Among the polymers defined above, mention may be made more particularlyof the dimethyldiallylammonium chloride homopolymer sold under the name“Merquat® 100” by the company Calgon (and its homologs of lowweight-average molecular mass) and the copolymers ofdiallyldimethylammonium chloride and of acrylamide, sold under the name“Merquat® 550”.

-   -   (7) The quaternary diammonium polymer containing repeating units        corresponding to the formula:

in which formula (VII):

-   -   R₁₀, R₁₁, R₁₂ and R₁₃, which may be identical or different,        represent aliphatic, alicyclic or arylaliphatic radicals        containing from 1 to 20 carbon atoms or lower        hydroxyalkylaliphatic radicals, or alternatively R₁₀, R₁₁, R₁₂        and R₁₃, together or separately, constitute, with the nitrogen        atoms to which they are attached, heterocycles optionally        containing a second hetero atom other than nitrogen, or        alternatively R₁₀, R₁₁, R₁₂ and R₁₃ represent a linear or        branched C₁–C₆ alkyl radical substituted with a nitrile, ester,        acyl or amide group or a group —CO—O—R₁₄-D or —CO—NH—R₁₄-D where        R₁₄ is an alkylene and D is a quaternary ammonium group;    -   A₁ and B₁ represent polymethylene groups containing from 2 to 20        carbon atoms which may be linear or branched, saturated or        unsaturated, and which may contain, linked to or intercalated in        the main chain, one or more aromatic rings or one or more oxygen        or sulfur atoms or sulfoxide, sulfone, disulfide, amino,        alkylamino, hydroxyl, quaternary ammonium, ureido, amide or        ester groups, and    -   X⁻ denotes an anion derived from an inorganic or organic acid;    -   A₁, R₁₀ and R₁₂ can form, with the two nitrogen atoms to which        they are attached, a piperazine ring; in addition, if A₁ denotes        a linear or branched, saturated or unsaturated alkylene or        hydroxyalkylene radical, B₁ can also denote a group        —(CH₂)_(n)—CO-D-OC—(CH₂)_(n)— in which n is between 1 and 100        and preferably between 1 and 50, and D denotes:    -   a) a glycol residue of formula: —O-Z-O—, where Z denotes a        linear or branched hydrocarbon-based radical or a group        corresponding to one of the following formulae:        —(CH₂—CH₂—O)—CH₂—CH₂—        —[CH₂—CH(CH₃)—O]_(y)—CH₂—CH(CH₃)—        where x and y denote an integer from 1 to 4, representing a        defined and unique degree of polymerization or any number from 1        to 4 representing an average degree of polymerization;    -   b) a bis-secondary diamine residue such as a piperazine        derivative;    -   c) a bis-primary diamine residue of formula: —NH—Y—NH—, where Y        denotes a linear or branched hydrocarbon-based radical, or        alternatively the divalent radical        —CH₂—CH₂—S—S—CH₂—CH₂—;    -   d) a ureylene group of formula: —NH—CO—NH—.

Preferably, X⁻ is an anion such as chloride or bromide.

These polymers generally have a number-average molecular mass of between1000 and 100 000.

Polymers of this type are described in particular in French patents 2320 330, 2 270 846, 2 316 271, 2 336 434 and 2 413 907 and U.S. Pat.Nos. 2,273,780, 2,375,853, 2,388,614, 2,454,547, 3,206,462, 2,261,002,2,271,378, 3,874,870, 4,001,432, 3,929,990, 3,966,904, 4,005,193,4,025,617, 4,025,627, 4,025,653, 4,026,945 and 4,027,020.

It is more particularly possible to use polymers that consist ofrepeating units corresponding to the following formula (VIII):

in which R₁₀, R₁₁, R₁₂ and R₁₃, which may be identical or different,denote an alkyl or hydroxyalkyl radical containing from 1 to 4 carbonatoms approximately, n and p are integers ranging from 2 to 20approximately, and X— is an anion derived from an inorganic or organicacid.

-   -   (8) Polyquaternary ammonium polymers consisting of units of        formula (IX)

in which:

-   -   p denotes an integer ranging from 1 to 6 approximately, D may be        nothing or may represent a group —(CH₂)_(r)—CO— in which    -   r denotes a number equal to 4 or 7, and    -   X⁻ is an anion derived from a mineral or organic acid.

The cationic polymers comprising units of formula (IX) are describedespecially in patent application EP-A-122 324 and may be preparedaccording to the processes described in U.S. Pat. Nos. 4,157,388,4,390,689, 4,702,906 and 4,719,282.

Among these polymers, the ones that are preferred are those with amolecular mass, measured by carbon-13 NMR of less than 100 000, and inthe formula of which:

-   -   p is equal to 3, and    -   a) D represents a —(CH₂)₄—CO— group, X denotes a chlorine atom,        the molecular mass measured by carbon-13 NMR (¹³C NMR) being        about 5 600;    -   a polymer of this type is sold by the company Miranol under the        name Mirapol-AD1,    -   b) D represents a —(CH₂)₇—CO— group, X denotes a chlorine atom,        the molecular mass measured by carbon-13 NMR (¹³C NMR) being        about 8 100; a polymer of this type is sold by the company        Miranol under the name Mirapol-AZ1,    -   c) D denotes the value zero, X denotes a chlorine atom, the        molecular mass measured by carbon-13 NMR (¹³C NMR) being about        25 500; a polymer of this type is sold by the company Miranol        under the name Mirapol-A15,    -   d) a “Block Copolymer” formed from units corresponding to the        polymers described in paragraphs a) to c), sold by the company        Miranol under the names Mirapol-9 (¹³C NMR molecular mass, about        7 800), Mirapol-175 (¹³C NMR molecular mass, about 8 000) and        Mirapol-95 (¹³C NMR molecular mass, about 12 500).

The polymer containing units of formula (IX) in which p is equal to 3, Ddenotes the value zero and X denotes a chlorine atom, the molecular massmeasured by carbon-13 NMR (¹³C NMR) being about 25 500, is even moreparticularly preferred according to the invention.

-   -   (9) Quaternary polymers of vinylpyrrolidone and of        vinylimidazole, such as, for example, the products sold under        the names Luviquat FC 905, FC 550 and FC 370 by the company        BASF.    -   (10) Polyamines such as Polyquart H sold by Henkel, which is        given under the reference name “Polyethylene glycol (15) tallow        polyamine” in the CTFA dictionary.    -   (11) Crosslinked methacryloyloxy(C₁–C₄) alkyltri        (C₁–C₄)-alkylammonium salt polymers such as the polymers        obtained by homopolymerization of dimethylaminoethyl        methacrylate quaternized with methyl chloride, or by        copolymerization of acrylamide with dimethylaminoethyl        methacrylate quaternized with methyl chloride, the homo- or        copolymerization being followed by crosslinking with a compound        containing olefinic unsaturation, in particular        methylenebisacrylamide. A crosslinked        acrylamide/methacryloyloxyethyltrimethylammonium chloride        copolymer (20/80 by weight) in the form of a dispersion        containing 50% by weight of said copolymer in mineral oil can be        used more particularly. This dispersion is sold under the name        “Salcare® SC 92” by the company Allied Colloids. A crosslinked        meth-acryloyloxyethyltrimethylammonium chloride homopolymer        containing about 50% by weight of the homopolymer in mineral oil        or in a liquid ester can also be used. These dispersions are        sold under the names “Salcare® SC 95” and “Salcare® SC 96” by        the company Allied Colloids.

Other cationic polymers which can be used in the context of theinvention are polyalkyleneimines, in particular polyethyleneimines,polymers containing vinylpyridine or vinylpyridinium units, condensatesof polyamines and of epichlorohydrin, quaternary polyureylenes andchitin derivatives.

Among all the cationic polymers which may be used in the context of thepresent invention, it is preferred to use the polymers of families (1),(6), (7), (8) and (11) and even more preferably the polymers containingrepeating units of formulae (W) and (U) below:

and in particular those whose molecular weight, determined by gelpermeation chromatography, is between 9500 and 9900;

and in particular those whose molecular weight, determined by gelpermeation chromatography, is about 1200.

The concentration of cationic polymer in the composition according tothe present invention may range from 0.01% to 10% by weight relative tothe total weight of the composition, preferably from 0.05% to 5% andeven more preferably from 0.1% to 3%.

Amphoteric Polymers

The amphoteric polymers that may be used in accordance with the presentinvention may be chosen from polymers comprising units K and M randomlydistributed in the polymer chain, in which K denotes a unit derived froma monomer comprising at least one basic nitrogen atom and M denotes aunit derived from an acidic monomer comprising one or more carboxylic orsulfonic groups, or alternatively K and M may denote groups derived fromzwitterionic carboxybetaine or sulfobetaine monomers;

-   -   K and M may also denote a cationic polymer chain comprising        primary, secondary, tertiary or quaternary amine groups, in        which at least one of the amine groups bears a carboxylic or        sulfonic group linked via a hydrocarbon-based radical, or        alternatively K and M form part of a chain of a polymer        containing an α,β-dicarboxylic ethylene unit in which one of the        carboxylic groups has been made to react with a polyamine        comprising one or more primary or secondary amine groups.

The amphoteric polymers corresponding to the above definition that aremore particularly preferred are chosen from the following polymers:

-   -   (1) polymers resulting from the copolymerization of a monomer        derived from a vinyl compound bearing a carboxylic group such        as, more particularly, acrylic acid, methacrylic acid, maleic        acid, α-chloroacrylic acid, and from a substituted vinyl        compound containing at least one basic atom, such as, more        particularly, dialkylaminoalkyl methacrylate and acrylate,        dialkylaminoalkylmethacrylamide and -acrylamide. Such compounds        are described in U.S. Pat. No. 3,836,537. Mention may also be        made of the sodium acrylate/acrylamidopropyltrimethylammonium        chloride copolymer sold under the name Polyquart KE 3033 by the        company Henkel.

The substituted vinyl compound containing at least one basic atom mayalso be a dialkyldiallylammonium salt such as dimethyldiallylammoniumchloride. The copolymers of acrylic acid and of the latter monomer aresold under the names Merquat 280, Merquat 295 and Merquat Plus 3330 bythe company Calgon.

-   -   (2) Polymers containing units derived from:    -   a) at least one monomer chosen from acrylamides and        methacrylamides substituted on the nitrogen with an alkyl        radical,    -   b) at least one acidic comonomer containing one or more reactive        carboxylic groups, and    -   c) at least one basic comonomer such as esters containing        primary, secondary, tertiary and quaternary amine substituents        of acrylic and methacrylic acids and the product of        quaternization of dimethylaminoethyl methacrylate with dimethyl        or diethyl sulfate.

The N-substituted acrylamides or methacrylamides which are moreparticularly preferred according to the invention are groups in whichthe alkyl radicals contain from 2 to 12 carbon atoms and moreparticularly N-ethylacrylamide, N-tert-butylacrylamide,N-tert-octylacrylamide, N-octylacrylamide, N-decylacrylamide,N-dodecylacrylamide and the corresponding methacrylamides.

The acidic comonomers are chosen more particularly from acrylic acid,methacrylic acid, crotonic acid, itaconic acid, maleic acid and fumaricacid and alkyl monoesters, having 1 to 4 carbon atoms, of maleic orfumaric acids or anhydrides.

The preferred basic comonomers are aminoethyl, butylaminoethyl,N,N′-dimethylaminoethyl and N-tert-butylaminoethyl methacrylates.

The copolymers whose CTFA (4th edition, 1991) name isOctylacrylamide/acrylates/butylaminoethyl methacrylate copolymer such asthe products sold under the name Amphomer or Lovocryl 47 by the companyNational Starch are particularly used.

-   -   (3) Polyamino amides that are crosslinked and alkylated        partially or totally derived from polyamino amides of general        formula:        CO—R₁₉—CO-Z          (X)        in which R₁₉ represents a divalent radical derived from a        saturated dicarboxylic acid, a mono- or dicarboxylic aliphatic        acid containing an ethylenic double bond, an ester of a lower        alkanol, having 1 to 6 carbon atoms, of these acids or a radical        derived from the addition of any one of said acids to a        bis(primary) or bis(secondary) amine, and Z denotes a        bis(primary), mono- or bis(secondary) polyalkylene-polyamine        radical and preferably represents:    -   a) in proportions of from 60 to 100 mol %, the radical

where x=2 and p=2 or 3, or alternatively x=3 and p=2 this radical beingderived from diethylenetriamine, from triethylenetetraamine or fromdipropylenetriamine;

-   -   b) in proportions of from 0 to 40 mol %, the radical (XI) above        in which x=2 and p=1 and which is derived from ethylenediamine,        or the radical derived from piperazine:

-   -   c) in proportions of from 0 to 20 mol %, the —NH—(CH₂)₆—NH—        radical derived from hexamethylenediamine, these polyamino        amines being crosslinked by addition of a difunctional        crosslinking agent chosen from epihalohydrins, diepoxides,        dianhydrides and bis-unsaturated derivatives, using from 0.025        to 0.35 mol of crosslinking agent per amine group of the        polyamino amide and alkylated by the action of acrylic acid,        chloroacetic acid or an alkane sultone, or salts thereof.

The saturated carboxylic acids are preferably chosen from acids having 6to 10 carbon atoms, such as adipic acid, 2,2,4-trimethyladipic acid and2,4,4-trimethyladipic acid, terephthalic acid and acids containing anethylenic double bond such as, for example, acrylic acid, methacrylicacid and itaconic acid.

The alkane sultones used in the alkylation are preferably propanesultone or butane sultone, and the salts of the alkylating agents arepreferably the sodium or potassium salts.

-   -   (4) Polymers containing zwitterionic units of formula:

in which R₂₀ denotes a polymerizable unsaturated group such as anacrylate, methacrylate, acrylamide or methacrylamide group, y and zrepresent an integer from 1 to 3, R₂₁ and R₂₂ represent a hydrogen atom,methyl, ethyl or propyl, R₂₃ and R₂₄ represent a hydrogen atom or analkyl radical such that the sum of the carbon atoms in R₂₃ and R₂₄ doesnot exceed 10.

The polymers comprising such units can also contain units derived fromnonzwitterionic monomers such as dimethyl or diethylaminoethyl acrylateor methacrylate or alkyl acrylates or methacrylates, acrylamides ormethacrylamides or vinyl acetate.

By way of example, mention may be made of the copolymer of butylmethacrylate/dimethyl carboxymethylammonio ethyl methacrylate such asthe product sold under the name Diaformer Z301 by the company Sandoz.

-   -   (5) Polymers derived from chitosan, described especially in        French patent No 2 137 684 or U.S. Pat. No. 3,879,376,        containing monomer units corresponding to formulae (XIII), (XIV)        and (XV) below connected in their chain:

the unit (XIII) being present in proportions of between 0 and 30%, theunit (XIV) in proportions of between 5 and 50% and the unit (XV) inproportions of between 30 and 90%, it being understood that, in thisunit (XV), R₂₅ represents a radical of formula:

in which q denotes zero or 1;

-   -   if q=0, R₂₆, R₂₇ and R₂₈, which may be identical or different,        each represent a hydrogen atom, a methyl, hydroxyl, acetoxy or        amino residue, a monoalkylamine residue or a dialkylamine        residue which are optionally interrupted by one or more nitrogen        atoms and/or optionally substituted with one or more amine,        hydroxyl, carboxyl, alkylthio or sulfonic groups, an alkylthio        residue in which the alkyl group bears an amino residue, at        least one of the radicals R₂₆, R₂₇ and R₂₈ being, in this case,        a hydrogen atom;    -   or, if q=1, R₂₆, R₂₇ and R₂₈ each represent a hydrogen atom, as        well as the salts formed by these compounds with bases or acids.    -   More particularly preferred polymers of this type comprise from        0 to 20% by weight of the units (XIII) , from 40 to 50% by        weight of units (XIV), and from 40 to 50% by weight of        units (XV) in which R₂₅ denotes the radical —CH₂—CH₂—;    -   (6) Polymers derived from the N-carboxyalkylation of chitosan,        such as N-carboxymethylchitosan or N-carboxybutylchitosan sold        under the name “Evalsan” by the company Jan Dekker.    -   (7) Polymers corresponding to the general formula (XI) as        described, for example, in French patent 1 400 366:

in which R₂₉ represents a hydrogen atom, a CH₃ _(O, CH) ₃CH₂O or phenylradical, R₃₀ denotes hydrogen or a lower alkyl radical such as methyl orethyl, R₃₁ denotes hydrogen or a lower alkyl radical such as methyl orethyl, R₃₂ denotes a lower alkyl radical such as methyl or ethyl or aradical corresponding to the formula: —R₃₃—N(R₃₁)₂, R₃₃ representing a—CH₂—CH₂—, —CH₂—CH₂—CH₂— or —CH₂—CH(CH₃)— group, R₃₁ having the meaningsmentioned above,

-   -   as well as the higher homologs of these radicals and containing        up to 6 carbon atoms,    -   r is such that the molecular weight is between 500 and 6 000 000        and preferably between 1000 and 1 000 000.    -   (8) Amphoteric polymers of the type -D-X-D-X— chosen from:    -   a) polymers obtained by the action of chloroacetic acid or        sodium chloroacetate on compounds containing at least one unit        of formula:        -D-X-D-X-D-   (XVII)        where D denotes a radical

and X denotes the symbol E or E′, E or E′, which may be identical ordifferent, denotes a divalent radical which is an alkylene radical witha straight or branched chain containing up to 7 carbon atoms in the mainchain, which is unsubstituted or substituted with hydroxyl groups andwhich can contain, in addition to the oxygen, nitrogen and sulfur atoms,1 to 3 aromatic and/or heterocyclic rings; the oxygen, nitrogen andsulfur atoms being present in the form of ether, thioether, sulfoxide,sulfone, sulfonium, alkylamine or alkenylamine groups, hydroxyl,benzylamine, amine oxide, quaternary ammonium, amide, imide, alcohol,ester and/or urethane groups;

-   -   b) polymers of formula:        -D-X-D-X—  (XVIII)        where D denotes a radical

and X denotes the symbol E or E′ and at least once E′; E having themeaning given above and E′ being a divalent radical which is an alkyleneradical with a straight or branched chain having up to 7 carbon atoms inthe main chain, which is unsubstituted or substituted with one or morehydroxyl radicals and containing one or more nitrogen atoms, thenitrogen atom being substituted with an alkyl chain which is optionallyinterrupted by an oxygen atom and necessarily containing one or morecarboxyl functions or one or more hydroxyl functions and betainized byreaction with chloroacetic acid or sodium chloroacetate.

-   -   (9) (C₁–C₅)alkyl vinyl ether/maleic anhydride copolymers        partially modified by semiamidation with an        N,N-dialkylaminoalkylamine such as N,N-dimethylaminopropylamine        or by semiesterification with an N,N-dialkanolamine. These        copolymers can also contain other vinyl comonomers such as        vinylcaprolactam.

The amphoteric polymers that are particularly preferred according to theinvention are those of family (1).

According to the invention, the amphoteric polymer(s) may represent from0.01% to 10% by weight, preferably from 0.05% to 5% by weight and evenmore preferably from 0.1% to 3% by weight relative to the total weightof the composition.

The compositions of the invention preferably comprise one or moresurfactants which can be chosen without preference, alone or asmixtures, from anionic, amphoteric, nonionic, zwitterionic and cationicsurfactants.

The surfactants that are suitable for carrying out the present inventionare, in particular, the following:

(i) Anionic Surfactant(s):

As examples of anionic surfactants which can be used, alone or asmixtures, in the context of the present invention, mention may be madein particular (nonlimiting list) of salts (in particular alkaline salts,especially sodium salts, ammonium salts, amine salts, amino alcoholsalts or magnesium salts) of the following compounds: alkyl sulfates,alkyl ether sulfates, alkylamido ether sulfates, alkylarylpolyethersulfates, monoglyceride sulfates; alkyl sulfonates, alkyl phosphates,alkylamide sulfonates, alkylaryl sulfonates, α-olefin sulfonates,paraffin sulfonates; (C₆–C₂₄)alkyl sulfosuccinates, (C₆–C₂₄)alkyl ethersulfosuccinates, (C₆–C₂₄)alkylamide sulfosuccinates; (C₆–C₂₄)alkylsulfoacetates; (C₆–C₂₄)acyl sarcosinates and (C₆–C₂₄)acyl glutamates. Itis also possible to use the carboxylic esters of(C₆–C₂₄)alkylpolyglycosides, such as alkylglucoside citrates,alkylpolyglycoside tartrates and alkylpolyglycoside sulfosuccinates,alkylsulfosuccinamates; acyl isethionates and N-acyltaurates, the alkylor acyl radical of all of these various compounds preferably containingfrom 12 to 20 carbon atoms, and the aryl radical preferably denoting aphenyl or benzyl group. Among the anionic surfactants which can also beused, mention may also be made of fatty acid salts such as the salts ofoleic, ricinoleic, palmitic and stearic acids, coconut oil acid orhydrogenated coconut oil acid; acyl lactylates in which the acyl radicalcontains 8 to 20 carbon atoms. Alkyl-D-galactosideuronic acids and theirsalts, polyoxyalkylenated (C₆–C₂₄)alkyl ether carboxylic acids,polyoxyalkylenated (C₆–C₂₄)alkylaryl ether carboxylic acids,polyoxyalkylenated (C₆–C₂₄)alkylamido ether carboxylic acids and theirsalts, in particular those containing from 2 to 50 alkylene oxide, inparticular ethylene oxide, groups, and mixtures thereof can also beused.

(ii) Nonionic Surfactant(s):

The nonionic surfactants are also compounds that are well known per se(see in particular in this respect “Handbook of Surfactants” by M. R.Porter, published by Blackie & Son (Glasgow and London), 1991, pp.116–178) and, in the context of the present invention, their nature isnot a critical feature. Thus, they can be chosen in particular from(nonlimiting list) polyethoxylated or polypropoxylated alkylphenols,α-diols or alcohols having a fatty chain containing, for example, 8 to18 carbon atoms, it being possible for the number of ethylene oxide orpropylene oxide groups to range in particular from 2 to 50. Mention mayalso be made of copolymers of ethylene oxide and of propylene oxide,condensates of ethylene oxide and of propylene oxide with fattyalcohols; polyethoxylated fatty amides preferably having from 2 to 30mol of ethylene oxide, polyglycerolated fatty amides containing onaverage 1 to 5, and in particular 1.5 to 4, glycerol groups;polyethoxylated fatty amines preferably having from 2 to 30 mol ofethylene oxide; oxyethylenated fatty acid esters of sorbitan having from2 to 30 mol of ethylene oxide; fatty acid esters of sucrose, fatty acidesters of polyethylene glycol, alkylpolyglycosides, N-alkylglucaminederivatives, amine oxides such as (C₁₀–C₁₄)alkylamine oxides orN-acylaminopropylmorpholine oxides. It will be noted that thealkylpolyglycosides constitute nonionic surfactants that areparticularly suitable in the context of the present invention.

(iii) Amphoteric or Zwitterionic Surfactant(s):

The amphoteric or zwitterionic surfactants, whose nature is not acritical feature in the context of the present invention, can be, inparticular (nonlimiting list), aliphatic secondary or tertiary aminederivatives in which the aliphatic radical is a linear or branched chaincontaining 8 to 18 carbon atoms and containing at least onewater-soluble anionic group (for example carboxylate, sulfonate,sulfate, phosphate or phosphonate); mention may also be made of(C₈–C₂₀)alkylbetaines, sulfobetaines, (C₈–C₂₀) alkylamido (C₁–C₆)alkylbetaines or (C₈–C₂₀) alkylamido (C₁–C₆) alkylsulfobetaines.

Among the amine derivatives, mention may be made of the products soldunder the name Miranol, as described in U.S. Pat. Nos. 2,528,378 and2,781,354 and classified in the CTFA dictionary, 3rd edition, 1982,under the names amphocarboxyglycinates and amphocarboxypropionates ofrespective structures:R₂—CONHCH₂CH₂—N(R₃)(R₄)(CH₂COO⁻)in which: R₂ denotes an alkyl radical of an acid R₂—COOH present inhydrolyzed coconut oil, a heptyl, nonyl or undecyl radical, R₃ denotes aβ-hydroxyethyl group and R₄ denotes a carboxymethyl group; andR₂′—CONHCH₂CH₂—N(B)(C)in which:

-   -   B represents —CH₂CH₂OX′, C represents —(CH₂)_(z)—Y′, with z=1 or        2,    -   X′ denotes a —CH₂CH₂—COOH group or a hydrogen atom,    -   Y′ denotes —COOH or a —CH₂—CHOH—SO₃H radical,    -   R₂′ denotes an alkyl radical of an acid R₉—COOH present in        coconut oil or in hydrolyzed linseed oil, an alkyl radical,    -   in particular a C₇, C₉, C₁₁ or C₁₃ alkyl radical, a C₁₇ alkyl        radical and its iso form, an unsaturated C₁₇ radical.

These compounds are classified in the CTFA dictionary, 5th edition,1993, under the names disodium cocoamphodiacetate, disodiumlauroamphodiacetate, disodium caprylamphodiacetate, disodiumcapryloamphodiacetate, disodium cocoamphodipropionate, disodiumlauroamphodipropionate, disodium caprylamphodipropionate, disodiumcapryloamphodipropionate, lauroamphodipropionic acid andcocoamphodipropionic acid.

By way of example, mention may be made of the cocoamphodiacetate soldunder the trade name Miranolo C2M Concentrate by the company RhodiaChimie.

(iv) Cationic Surfactants:

Among the cationic surfactants that may be mentioned in particular(nonlimiting list) are: primary, secondary or tertiary fatty aminesalts, optionally polyoxyalkylenated; quaternary ammonium salts such astetraalkylammonium, alkylamidoalkyltrialkylammonium,trialkylbenzylammonium, trialkylhydroxyalkylammonium or alkylpyridiniumchlorides or bromides; imidazoline derivatives; or amine oxides ofcationic nature.

The amounts of surfactants present in the composition according to theinvention can range from 0.01% to 40% and preferably from 0.5% to 30%relative to the total weight of the composition.

Needless to say, a person skilled in the art will take care to selectthe optional additional compound(s) mentioned above such that theadvantageous properties intrinsically associated with the dyecomposition according to the invention are not, or are notsubstantially, adversely affected by the envisaged addition(s).

In the ready-to-use composition with oxidizing agent, the oxidizingagent is preferably chosen from hydrogen peroxide, urea peroxide, alkalimetal bromates or ferricyanides, and persalts such as perborates andpersulfates. It is particularly preferred to use hydrogen peroxide. Thisoxidizing agent advantageously consists of an aqueous hydrogen peroxidesolution whose titer may range, more particularly, from about 1 to 40volumes and even more preferably from about 5 to 40 volumes.

Oxidizing agents that may also be used are one or more redox enzymessuch as laccases, peroxidases and 2-electron oxidoreductases (such asuricase), where appropriate in the presence of their respective donor orcofactor.

The pH of the composition [composition with or without oxidizing agent]is generally between 2 and 12. It is preferably between 3 and 11 andmore particularly between 7 and 10. It may be adjusted to the desiredvalue using acidifying or basifying agents or buffers that are wellknown in the prior art in the dyeing of keratin fibers.

More preferably, when the composition contains an oxidizing agent forlightening fibers, the pH of the ready-to-use mixture is greater than 7and even more preferably greater than 8.

Among the basifying agents that may be mentioned, for example, areaqueous ammonia, alkali metal carbonates, alkanolamines such asmonoethanolamine, diethanolamine and triethanolamine and alsoderivatives thereof, oxyethylenated and/or oxypropylenatedhydroxyalkylamines and ethylene-diamines, sodium hydroxide, potassiumhydroxide and the compounds of formula (XIX) below:

in which R is a propylene residue optionally substituted with a hydroxylgroup or a C₁–C₄ alkyl radical; R₃₈, R₃₉, R₄₀ and R₄₁, which may beidentical or different, represent a hydrogen atom, a C₁–C₄ alkyl radicalor a C₁–C₄ hydroxyalkyl radical.

The acidifying agents are conventionally, for example, mineral ororganic acids, for instance hydrochloric acid, orthophosphoric acid,carboxylic acids, for instance tartaric acid, citric acid or lacticacid, or sulfonic acids.

Among the buffers that may be mentioned are those sold by the companyMerck under the brand name Titrisol, such as the phosphate buffer(KH₂PO₄ at 0.026 mol/l, Na₂HPO₄ at 0.041 mol/l) and the borate buffer(H₃BO₃ at 0.05 mol/l, KCl at 0.05 mol/l, NaOH at 0.022 mol/l).

The dyeing process according to the invention is performed at roomtemperature and consists in applying the dye composition according tothe invention (prepared extemporaneously at the time of use) with orwithout oxidizing agent, onto wet or dry keratin fibers, and in leavingit to act for a leave-in time ranging from 5 seconds to 60 minutesapproximately, more preferably from 10 seconds to 5 minutesapproximately and more particularly from 30 seconds to 2 minutesapproximately, rinsing the fibers and then optionally washing them withshampoo, followed by rinsing them again and drying them.

The process according to the invention has the advantage of requiringonly very short application times, of about from 10 seconds to 5 minutesand more particularly from 30 seconds to 2 minutes.

It is possible to perform the process at higher temperatures, such asthose produced by a hairstyling hood, about 40° C., or by blow-drying,about 70–80° C.

Concrete examples illustrating the invention are given below, without,however, having any limiting nature.

EXAMPLES 1 and 2

The direct dye compositions below were prepared:

EXAMPLE 1 2 Nitro direct dye: 0.364 1-β-hydroxyethyloxy-3-methylamino-4-nitrobenzene (1-Methyl-1-phenyl)-2-(1-methine-4N- 0.364methylpyridinylium)hydrazine methyl sulfate Dicationic compound offormula (I) 1 0.423 0.212 Hydroxyethylcellulose 0.378 0.384 Surfactant:2.95 3 (50/50 C8/C10)alkyl polyglucoside as an aqueous 60% solutionPolyethylene glycol (8EO) 5.906 6 Benzyl alcohol 3.938 4 Preservingagent: 0.0032 0.0032 methyl, butyl, ethyl, propyl, and isobutylp-hydroxybenzoate pH 9 borate buffer 49.99 50 Demineralized water q.s.100 100 [amounts expressed as grams of Active Material (AM)]

Each of the compositions of examples 1 and 2 was applied to locks ofnatural gray hair containing 90% white hairs, for 20 minutes at roomtemperature (20° C.).

After the leave-in time, the locks of hair were rinsed and then dried.They were dyed in a matt [lacuna] shade with the composition of example1 and a violet shade with the composition of example 2, and showedlittle selectivity and good resistance to washing.

EXAMPLE 3

The lightening direct dye composition below was prepared:

EXAMPLE 3 Hydroxyethylcellulose 1.39 Aqueous ammonia (40% NH₄OH) 2.0840-volumes aqueous hydrogen peroxide 60 solution Dicatonic compound offormula (I) 1 0.268 (1-Methyl-1-phenyl)-2-(1-methine-4N- 0.230methylpyridinylium)hydrazine methyl sulfate Demineralized water q.s. 100[amounts expressed as grams of Active Material (AM)]

The composition was applied to locks of natural gray hair containing 90%white hairs, for 35 minutes at room temperature (20° C.).

After the leave-in time, the locks of hair were rinsed and then dried.They were dyed in a matt yellow shade that showed little selectivity andgood resistance to washing.

1. A dye composition for human keratin fibers, comprising, in a mediumthat is suitable for dyeing, at least one direct dye, and at least onedicationic compound chosen from those of formulae (I), (II) and (III):

wherein: A and A1, which may be identical or different, are chosen fromradicals of formula (a)

Z is chosen from aliphatic and aromatic radicals, Z₁ is an alkylradical, R₁ and R₂, which may be identical or different, are chosen fromhydrogen atoms, (C₁–C₄)alkyl radicals optionally substituted with atleast one entity chosen from halogen atoms, hydroxyl, carboxyl and cyanoradicals; (C₁–C₄)alkoxy radicals optionally substituted with at leastone radical chosen from hydroxyl and (C₁–C₄)alkoxy radicals; and amino,alkylamino, dialkylamino, aminocarbonyl, phenyl, phenoxy andphenylaminocarbonyl radicals, wherein the phenyl radicals are optionallysubstituted with at least one radical chosen from (C₁–C₄)alkyl,(C₁–C₄)alkoxy and phenoxy radicals, or R₁ and R₂ can form, together withthe two nitrogen atoms that bear them and the radical Z, a piperazinering, X is a bridging radical chosen from —CO—; —CO—CH₂—CH₂—CO—;—CO—CO—; 1,4-dicarbonylphenyl; —CH₂—CH₂—; and triazines of formulae (b)and (c):

wherein: Y and Y₁, which may be identical or different, are chosen fromhalogen atoms and hydroxyl, amino, monoalkylamino, dialkylamino,1-piperidino, morpholino and 1-piperazino radicals, wherein thepiperazino radicals are optionally substituted on the nitrogen atom notattached to the triazine ring with at least one (C₁–C₄)alkyl radical,said alkyl radicals being optionally substituted with at least oneradical chosen from hydroxyl, amino, mono(C₁–C₄)alkylamino anddi(C₁–C₄)alkylamino radicals, Z₂ is chosen from (C₂–C₈)alkyleneradicals, or alternatively, forms a piperazine ring with the twoadjacent nitrogen atoms and the radicals R₁ and R₂, R₃ and R₄, which maybe identical or different, are chosen from hydrogen atoms, (C₁–C₄)alkylradicals optionally substituted with at least one entity chosen fromhalogen atoms, hydroxyl, carboxyl, and cyano radicals; (C₁–C₄)alkoxyradicals optionally substituted with at least one radical chosen fromhydroxyl and (C₁–C₄)alkoxy radicals; and amino, alkylamino,dialkylamino, aminocarbonyl, phenyl, phenoxy and phenylaminocarbonylradicals, wherein the phenyl radicals are optionally substituted with atleast one radical chosen from (C₁–C₄)alkyl, (C₁–C₄)alkoxy and phenoxyradicals, —R₅ and R₆, which may be identical or different, are chosenfrom hydrogen atoms; (C₁–C₄)alkoxy radicals optionally substituted withat least one radical chosen from hydroxyl, carboxyl, halogen and cyanoradicals; (C₁–C₄)alkoxy radicals optionally substituted with at leastone radical chosen from hydroxyl and (C₁–C₄)alkoxy radicals; and amino,alkylamino, dialkylamino, aminocarbonyl, phenyl, phenoxy andphenylaminocarbonyl radicals, wherein the phenyl radicals are optionallysubstituted with at least one radical chosen from (C₁–C₄)alkyl,(C₁–C₄)alkoxy and phenoxy radicals, An⁻ denotes an anion; X′ and Y′,which may be identical or different, are chosen from hydrogen andhalogen atoms, and (C₁–C₄)alkyl, (C₁–C₄)alkoxy,(C₁–C₄)alkylcarbonylamino, arylcarbonylamino, ureido and arylureidoradicals, R′₁ is chosen from hydrogen atoms, optionally substitutedalkyl and aryl radicals, and R′₂ radicals, R′₂ is a radical of formula(d):

wherein: B is chosen from linear and branched alkylene radicals, R′₆ ischosen from hydrogen atoms and optionally substituted alkyl radicals,R′₇ and R′₈, which may be identical or different, are chosen fromoptionally substituted alkyl radicals, R′₆ and R′₇, together with thenitrogen, form an optionally substituted 5-, 6- or 7-membered ring,which may comprise other hetero atoms, or alternatively R′₆, R′₇ and R′₈together form a pyridinium ring, R′₃ is chosen from hydrogen and halogenatoms, and (C₁–C₄)alkyl (C₁–C₄)alkoxy radicals, W is a radical offormula (e):

wherein: K is a coupling radical, Z is a bridging radical chosen fromthe radicals of formulae:

and —CO—NR′₉—B₁—NR′₉—CO—, and wherein R′₉ is chosen from hydrogen atomsand optionally substituted (C₂–C₄)alkyl radicals, and a B₁ is chosenfrom linear and branched C₂–C₁₂ alkylene radicals optionally interruptedwith at least one entity chosen from —NR′₉— radicals, and oxygen andsulfur atoms; and wherein, in formula (III), the number of cationiccharges is two.
 2. The composition according to claim 1, wherein thehuman keratin fibers are hair.
 3. The composition according to claim 1,wherein, in formula (I), R₁ and R₂, which may be identical or different,are chosen from hydrogen atoms, (C₁–C₄)alkyl radicals substituted withhydroxyl radicals and (C₁–C₄)alkoxy radicals, Z is chosen from linear,branched and cyclic C₂–C₈ alkyl radicals optionally substituted with atleast one entity chosen from hydroxyl and alkoxy radicals and halogenatoms, the chain of said radical optionally being interrupted with anentity chosen from oxygen atoms and —NR₁— groups; and 1,4-phenylradicals, 1,4-naphthyl radicals optionally substituted with at least oneentity chosen from alkyl and alkoxy radicals and halogen atoms; Zpossibly forming a piperazine ring together with R₁, R₂ and the twonitrogen atoms, X is chosen from groups of formula (b).
 4. Thecomposition according to claim 3, wherein R₁ and R₂, which may beidentical or different, are chosen from hydrogen atoms and methylradicals.
 5. The composition according to claim 3, wherein Z is chosenfrom unsubstituted phenyl radicals; phenyl and naphthyl radicalssubstituted with at least one entity chosen from methyl and methoxyradicals; piperazine radicals formed by bonding with R₁, R₂ and the twonitrogen atoms; and (C₂–C₄)alkylene radicals which are optionallysubstituted with at least one hydroxyl radical.
 6. The compositionaccording to claim 1, wherein, in formula (II): Z₁ is chosen fromlinear, branched and cyclic C₂–C₈ alkyl radicals, optionally substitutedwith at least one entity chosen from hydroxyl and alkoxy radicals andhalogen atoms, the chain of said radical optionally being interruptedwith an entity chosen from oxygen atoms and —NR₁— groups; and apiperazine ring formed with R₁, R₂ and the two nitrogen atoms, R₃ and R₄are chosen from methyl and ethyl radicals, and R₅ and R₆ are chosen fromhydrogen atoms, and methyl and methoxy radicals.
 7. The compositionaccording to claim 6, wherein Z₁ is chosen from (C₂–C₆)alkylene radicalsoptionally substituted with at least one hydroxyl group; and apiperazine ring formed with R₁, R₂ and the two nitrogen atoms,
 8. Thecomposition according to claim 7, wherein Z₁ is chosen fromunsubstituted (C₂–C₄)alkylene radicals.
 9. The composition according toclaim 1, wherein, in formula (III): B of formula (d) is chosen fromethylene, n-propylene, isopropylene and n-butylene radicals, K offormula (e) is a coupling compound chosen from those of formulae (f),(g) and (h):

wherein, X′, Y′ and R′₁, R′₂, and R′₃ have the same meaning as informula (III), n is equal to 1 or 2, and K₁ is a radical of formula:


10. A dye composition for human keratin fibers, comprising, in a mediumthat is suitable for dyeing, at least one direct dye, provided that thedirect dye is not chosen from Basic Blue 7, Basic Blue 26, Basic Blue99, Basic Violet 10, Basic Violet 14, Basic Brown 16, Basic Brown 17,Basic Red 2, Basic Red 22, Basic Red 76, Basic Red 118, and Basic Yellow57, and at least one dicationic compound of formula (IV):

wherein, in formula (IV): the groups [—NH-A-CH═CH—B] may be identical ordifferent, and wherein A is chosen from optionally substituted benzenerings, B is chosen from radicals derived from heterocyclic compoundscomprising a quaternized nitrogen comprising an entity chosen fromactive methyl and methylene radicals, R is the residue of a crosslinkingagent chosen from phosgene, halogenated triazines and halogenatedpyrimidines.
 11. The dye composition according to claim 10, wherein, informula (IV), B is chosen from quinolinium, picolinium, benzothiazolium,benzimidazolium, indolium and quinoxalinium derivatives; A is chosenfrom benzene rings that are optionally substituted with at least oneradical chosen from (C₁–C₄)alkoxy radicals, (C₁–C₄)alkyl radicals andhalogen atoms; and R is halogenated triazine chosen from2,4,6-trichlorotriazine, 2,4,6-trifluorotriazine,2,4-dichloro-6-(dimethylaminopropylamino)triazine,2,4-dichloro-6-hydroxytriazine,2,4-difluoro-6-(trimethylaminoethylamino)triazine chloride,2,4-difluoro-6-(N-carboxymethylamino)triazine,2,4-dichloro-6-(N,N-dihydroxyethylamino)triazine,2,4-difluoro-6-(N-hydroxypropylamino)triazine,2,4-dichloro-6-(N,N-dimethylamino)triazine,2,4-difluoro-6-(N,N-dihexylamino)triazine and2,4-dichloro-6-(N-2-sulfoethylamino)triazine.
 12. The dye compositionaccording to claim 1, wherein the at least one compound of formula (I)is chosen from those of formulae (I)1 to (I)7:


13. The dye composition according to claim 1, wherein the at least onecompound of formula (Ill) is the following compound:


14. The dye composition according to claim 10, wherein the at least onedicationic compound of formula (IV) is the following compound:


15. The dye composition according to claim 1, wherein the at least onedicationic compound chosen from those of formulae (I), (II), and (Ill)is present in an amount ranging from 0.01 % to 40% by weight, relativeto the total weight of the composition.
 16. The dye compositionaccording to claim 10, wherein the at least one dicationic compound offormula (IV) is present in an amount ranging from 0.01 % to 40% byweight, relative to the total weight of the composition.
 17. The dyecomposition according to claim 1, wherein the at least one direct dye ischosen from neutral, acidic and cationic nitrobenzene direct dyes;neutral, acidic and cationic azo direct dyes; quinone direct dyes; azinedirect dyes; triarylmethane direct dyes; indoamine direct dyes; cationicdirect dyes comprising a quaternized nitrogen atom and a —CH═N— bond;and natural direct dyes.
 18. The dye composition according to claim 17,wherein the at least one quinone direct dye is chosen from neutral,acidic and cationic anthraquinones.
 19. The dye composition according toclaim 1, wherein the at least one direct dye is present in an amountranging from 0.001% to 20% by weight, relative to the total weight ofthe composition.
 20. The dye composition according to claim 1, furthercomprising, in an amount ranging from 0.01% to 10% by weight, relativeto the total weight of the composition, at least one cationic oramphoteric polymer chosen from: dimethyldiallylammonium chloridehomopolymers; polymers comprising repeating units of formula (W) and(U):

polymers comprising units of formula (IX):

wherein p is equal to 3, D is chosen from a bond, —(CH₂)₄—CO— groups,—(CH₂)₇—CO— group groups, and X is a chlorine atom, or, alternatively, Dmay be chosen from block copolymers formed from units corresponding tothe polymers when D is chosen from a bond and —(CH₂)₄—CO— groups; andcopolymers of acrylic acid and of dimethyldiallylammonium chloride. 21.The dye composition according to claim 10, further comprising, in anamount ranging from 0.01% to 10% by weight, relative to the total weightof the composition, at least one cationic or amphoteric polymer chosenfrom: dimethyldiallylammonium chloride homopolymers; polymers comprisingrepeating units of formula (W) and (U):

polymers comprising units of formula (IX):

wherein p is equal to 3, D is chosen from a bond, —(CH₂)₄—CO— groups,—(CH₂)₇—CO— group groups, and X is a chlorine atom, or, alternatively, Dmay be chosen from block copolymers formed from units corresponding tothe polymers when D is chosen from a bond and —(CH₂)₄—CO— groups; andcopolymers of acrylic acid and of dimethyidiallylammonium chloride. 22.The dye composition according to claim 1, further comprising at leastone surfactant chosen from anionic, cationic, nonionic and amphotericsurfactants.
 23. The dye composition according to claim 10, furthercomprising at least one surfactant chosen from anionic, cationic,nonionic and amphoteric surfactants.
 24. A process for dyeing humankeratin fibers, comprising applying to the keratin fibers, which may bedry or wet, a dye composition comprising, in a medium that is suitablefor dyeing, at least one direct dye, and at least one dicationiccompound chosen from those of formulae (I), (II) and (III):

wherein: A and A1, which may be identical or different, are chosen fromradicals of formula (a)

Z is chosen from aliphatic and aromatic radicals, Z₁ is an alkylradical, R₁ and R₂, which may be identical or different, are chosen fromhydrogen atoms, (C₁–C₄)alkyl radicals optionally substituted with atleast one entity chosen from halogen atoms, hydroxyl, carboxyl and cyanoradicals; (C₁–C₄)alkoxy radicals optionally substituted with at leastone radical chosen from hydroxyl and (C₁–C₄)alkoxy radicals; and amino,alkylamino, dialkylamino, aminocarbonyl, phenyl, phenoxy andphenylaminocarbonyl radicals, wherein the phenyl radicals are optionallysubstituted with at least one radical chosen from (C₁–C₄)alkyl,(C₁–C₄)alkoxy and phenoxy radicals, or R₁ and R₂ can form, together withthe two nitrogen atoms that bear them and the radical Z, a piperazinering, X is a bridging radical chosen from —CO—; —CO—CH₂—CH₂—CO—;—CO—CO—; 1,4-dicarbonylphenyl; —CH₂—CH₂—; and triazines of formulae (b)and (c):

wherein: Y and Y₁, which may be identical or different, are chosen fromhalogen atoms and hydroxyl, amino, monoalkylamino, dialkylamino,1-piperidino, morpholino and 1-piperazino radicals, wherein thepiperazino radicals are optionally substituted on the nitrogen atom notattached to the triazine ring with at least one (C₁–C₄)alkyl radical,said alkyl radicals being optionally substituted with at least oneradical chosen from hydroxyl, amino, mono(C₁–C₄)alkylamino anddi(C₁–C₄)alkylamino radicals, Z₂ is chosen from (C₂–C₈)alkyleneradicals, or alternatively, forms a piperazine ring with the twoadjacent nitrogen atoms and the radicals R₁ and R₂, R₃ and R₄, which maybe identical or different, are chosen from hydrogen atoms, (C₁–C₄)alkylradicals optionally substituted with at least one entity chosen fromhalogen atoms, hydroxyl, carboxyl, and cyano radicals; (C₁–C₄)alkoxyradicals optionally substituted with at least one radical chosen fromhydroxyl and (C₁–C₄)alkoxy radicals; and amino, alkylamino,dialkylamino, aminocarbonyl, phenyl, phenoxy and phenylaminocarbonylradicals, wherein the phenyl radicals are optionally substituted with atleast one radical chosen from (C₁–C₄)alkyl, (C₁–C₄)alkoxy and phenoxyradicals, R₅ and R₆, which may be identical or different, are chosenfrom hydrogen atoms; (C₁–C₄)alkoxy radicals optionally substituted withan entity chosen from hydroxyl, carboxyl, halogen and cyano radicals;(C₁–C₄)alkoxy radicals optionally substituted with at least one radicalchosen from hydroxyl and (C₁–C₄)alkoxy radicals; and amino, alkylamino,dialkylamino, aminocarbonyl, phenyl, phenoxy and phenylaminocarbonylradicals, wherein the phenyl radicals are optionally substituted with atleast one radical chosen from (C₁–C₄)alkyl, (C₁–C₄)alkoxy and phenoxyradicals, An⁻ denotes an anion; X′ and Y′, which may be identical ordifferent, are chosen from hydrogen and halogen atoms, and (C₁–C₄)alkyl,(C₁–C₄)alkoxy, (C₁–C₄)alkylcarbonylamino, arylcarbonylamino, ureido andarylureido radicals, R′₁ is chosen from hydrogen atoms, optionallysubstituted alkyl and aryl radicals, and R′₂ radicals, R′₂ is a radicalof formula (d):

wherein: B is chosen from linear and branched alkylene radicals, R′₆ ischosen from hydrogen atoms and optionally substituted alkyl radicals,R′₇ and R′₈, which may be identical or different, are chosen fromoptionally substituted alkyl radicals, R′₆ and R′₇, together with thenitrogen, form an optionally substituted 5-, 6- or 7-membered ring,which may comprise other hetero atoms, or alternatively R′₆, R′₇ and R′₈together form a pyridinium ring, R′₃ is chosen from hydrogen and halogenatoms, and (C₁–C₄)alkyl (C₁–C₄)alkoxy radicals, W is a radical offormula (e):

wherein: K is a coupling radical, Z is a bridging radical chosen fromthe radicals of formulae:

and —CO—NR′₉—B₁—NR′₉—CO—, and wherein R′₉ is chosen from hydrogen atomsand optionally substituted (C₂–C₄)alkyl radicals, and B₁ is chosen fromlinear and branched C₂–C₁₂ alkylene radicals optionally interrupted withat least one entity chosen from —NR′₉— radicals, and oxygen and sulfuratoms; and wherein, in formula (III), the number of cationic charges istwo; leaving the dye composition to act on the keratin fibers for aleave-in time ranging from 5 seconds to 60 minutes; rinsing the keratinfibers and optionally washing the keratin fibers with shampoo, followedby rinsing them again and drying them.
 25. A process for dyeing humankeratin fibers comprising applying to the keratin fibers, which may bedry or wet, a composition comprising, in a medium that is suitable fordyeing, at least one direct dye, provided that the at lest one directdye is not chosen from the basic dyes, and at least one dicationiccompound of formula (IV):

wherein, in formula (IV): the groups [—NH-A-CH═CH—B] may be identical ordifferent, and wherein A is chosen from optionally substituted benzenerings, B is chosen from radicals derived from heterocyclic compoundscomprising a quaternized nitrogen comprising an entity chosen fromactive methyl and methylene radicals, R is the residue of a crosslinkingagent chosen from phosgene, halogenated triazines and halogenatedpyrimidines; leaving the dye composition to act on the keratin fibersfor a leave-in time ranging from 5 seconds to 60 minutes; rinsing thekeratin fibers and optionally washing the keratin fibers with shampoo,followed by rinsing them again and drying them.
 26. The processaccording to claim 24, wherein the dye composition further comprises atleast one oxidizing agent.
 27. The process according to claim 26,wherein the at least one oxidizing agent is mixed with the dyecomposition just before application to the keratin fibers.
 28. Theprocess according to claim 25, wherein the dye composition furthercomprises at least one oxidizing agent.
 29. The process according toclaim 28, wherein the at least one oxidizing agent is mixed with the dyecomposition just before application to the keratin fibers.
 30. Amulti-compartment kit for the direct lightening dyeing of human keratinfibers, comprising at least one first compartment comprising, in amedium that is suitable for dyeing, at least one direct dye, and atleast one dicationic compound chosen from those of formulae (I), (II)and (III):

wherein: A and A1, which may be identical or different, are chosen fromradicals of formula (a)

Z is chosen from aliphatic and aromatic radicals, Z₁ is an alkylradical, R₁ and R₂, which may be identical or different, are chosen fromhydrogen atoms, (C₁–C₄)alkyl radicals optionally substituted with atleast one entity chosen from halogen atoms, hydroxyl, carboxyl and cyanoradicals; (C₁–C₄)alkoxy radicals optionally substituted with at leastone radical chosen from hydroxyl and (C₁–C₄)alkoxy radicals; and amino,alkylamino, dialkylamino, aminocarbonyl, phenyl, phenoxy andphenylaminocarbonyl radicals, wherein the phenyl radicals are optionallysubstituted with at least one radical chosen from (C₁–C₄)alkyl,(C₁–C₄)alkoxy and phenoxy radicals, or R₁ and R₂ can form, together withthe two nitrogen atoms that bear them and the radical Z, a piperazinering, X is a bridging radical chosen from —CO—; —CO—CH₂—CH₂—CO—;—CO—CO—; 1,4-dicarbonylphenyl; —CH₂—CH₂—; and triazines of formulae (b)and (c):

wherein: Y and Y₁, which may be identical or different, are chosen fromhalogen atoms and hydroxyl, amino, monoalkylamino, dialkylamino,1-piperidino, morpholino and 1-piperazino radicals, wherein thepiperazino radicals are optionally substituted on the nitrogen atom notattached to the triazine ring with at least one (C₁–C₄)alkyl radical,said alkyl radicals being optionally substituted with at least oneradical chosen from hydroxyl, amino, mono(C₁–C₄)alkylamino anddi(C₁–C₄)alkylamino radicals, Z₂ is chosen from (C₂–C₈)alkyleneradicals, or alternatively, forms a piperazine ring with the twoadjacent nitrogen atoms and the radicals R₁ and R₂, R₃ and R₄, which maybe identical or different, are chosen from hydrogen atoms, (C₁–C₄)alkylradicals optionally substituted with at least one entity chosen fromhalogen atoms, hydroxyl, carboxyl, and cyano radicals; (C₁–C₄)alkoxyradicals optionally substituted with at least one radical chosen fromhydroxyl and (C₁–C₄)alkoxy radicals; and amino, alkylamino,dialkylamino, aminocarbonyl, phenyl, phenoxy and phenylaminocarbonylradicals, wherein the phenyl radicals are optionally substituted with atleast one radical chosen from (C₁–C₄)alkyl, (C₁–C₄)alkoxy and phenoxyradicals, R₅ and R₆, which may be identical or different, are chosenfrom hydrogen atoms; (C₁–C₄)alkoxy radicals optionally substituted withan entity chosen from hydroxyl, carboxyl, halogen and cyano radicals;(C₁–C₄)alkoxy radicals optionally substituted with at least one radicalchosen from hydroxyl and (C₁–C₄)alkoxy radicals; and amino, alkylamino,dialkylamino, aminocarbonyl, phenyl, phenoxy and phenylaminocarbonylradicals, wherein the phenyl radicals are optionally substituted with atleast one radical chosen from (C₁–C₄)alkyl, (C₁–C₄)alkoxy and phenoxyradicals, An⁻ denotes an anion; X′ and Y′, which may be identical ordifferent, are chosen from hydrogen and halogen atoms, and (C₁–C₄)alkyl,(C₁–C₄)alkoxy, (C₁–C₄)alkylcarbonylamino, arylcarbonylamino, ureido andarylureido radicals, R′₁ is chosen from hydrogen atoms, optionallysubstituted alkyl and aryl radicals, and R′₂ radicals, R′₂ is a radicalof formula (d):

wherein: B is chosen from linear and branched alkylene radicals, R′₆ ischosen from hydrogen atoms and optionally substituted alkyl radicals,R′₇ and R′₈, which may be identical or different, are chosen fromoptionally substituted alkyl radicals, R′₆ and R′₇, together with thenitrogen, form an optionally substituted 5-, 6- or 7-membered ring,which may comprise other hetero atoms, or alternatively R′₆, R′₇ and R′₈together form a pyridinium ring, R′₃ is chosen from hydrogen and halogenatoms, and (C₁–C₄)alkyl (C₁–C₄)alkoxy radicals, W is a radical offormula (e):

wherein: K is a coupling radical, Z is a bridging radical chosen fromthe radicals of formulae:

and —CO—NR′₉—B₁—NR′₉—CO—, and wherein R′₉ is chosen from hydrogen atomsand optionally substituted (C₂–C₄)alkyl radicals, and B₁ is chosen fromlinear and branched C₂–C₁₂ alkylene radicals optionally interrupted withat least one entity chosen from —NR′₉— radicals, and oxygen and sulfuratoms; and wherein, in formula (III), the number of cationic charges istwo; and at least one second compartment comprising at least oneoxidizing agent.
 31. A multi-compartment kit for the direct lighteningdyeing of human keratin fibers, comprising at least one firstcompartment comprising, in a medium suitable for dyeing, at least onedirect dye, provided that the at least one direct dye is not chosen fromthe basic dyes, and at least one dicationic compound of formula (IV):

wherein, in formula (IV): the groups [—NH-A-CH═CH—B] may be identical ordifferent, and wherein A is chosen from optionally substituted benzenerings, B is chosen from radicals derived from heterocyclic compoundscomprising a quaternized nitrogen comprising an entity chosen fromactive methyl and methylene radicals, R is the residue of a crosslinkingagent chosen from phosgene, halogenated triazines and halogenatedpyrimidine; and at least one second compartment comprising at least oneoxidizing agent.